Gus Atkinson finished with figures of 4-67, while Chris Woakes took 3-69 for England, as only a fine sixth-wicket stand from Jason Holder and Joshua Da Silva saved West Indies from being bowled out for a much lower total.
But England, chasing a 3-0 series whitewash, let their dominant position slip when taking up the bat for the final 35 minutes, Zak Crawley (18), Ben Duckett (3) and Mark Wood (0) being dispatched as bowler Jayden Seales dropped them to 38-3.
Windies skipper Kraigg Brathwaite won the toss and chose to bat, leading his side to a solid start before a spell of three wickets in five overs before lunch put England on top.
Atkinson accounted for Mikyle Louis (26) and Alick Athanaze (2) on either side of Wood sending stumps flying with a full delivery to dismiss Kirk McKenize for 12.
Brathwaite's knock of 61 was brought to a halt shortly after the action resumed, the captain gloving Wood's leg-side ball to Jamie Smith as the tourists slid from 76-0 to 115-5 in 45 balls.
Holder (59) and Da Silva (49) then shared 108 to drag the Windies towards a respectable total, but things looked bleak for them when the latter feathered Woakes' ball through to Smith.
Having gone 30 overs without a wicket, England needed just 14 more to polish off the tail, the highlight being a terrific diving catch from Joe Root to send Gudakesh Motie (8) packing.
England were given just over half an hour with the bat to cap Friday's action, but any hopes of a serene finish were soon dashed.
Holder made two terrific catches off Seales' bowling, the first from Crawley's thick outside edge and the second to dismiss Wood for a duck, either side of Alzarri Joseph's cracking delivery accounting for Duckett.
That spell ensured what had been a good day for the hosts ended on a sour note, with the Windies sure to target quick wickets when the action resumes on Saturday.
Data Debrief: Atkinson and Seales dominate
This series began with all the focus on James Anderson as England's greatest-ever bowler bowed out at Lord's, but Atkinson has taken centre-stage since making his Test debut in the opening match and now has 20 wickets through five innings.
That is eight more than West Indies' Jayden Seales, the next-most prolific bowler in this series, has managed.
Seales was determined to have an impact on day one, though, and his two wickets at the death have set the stage for a far more competitive match than those England won at Lord's and Trent Bridge.
The wicket-keeper-batter hit an impressive 95 off 109 balls, falling just shy of his maiden century in only his third Test.
Chasing the Windies' first-innings total of 282, England made a nervy start with the early wickets of Ollie Pope (10) and Harry Brook (two) leaving them at 54-5.
Joe Root (87) and Ben Stokes (54) settled the hosts down with a 115-run stand, while Smith's near-century and 62 from Chris Woakes helped them to a total of 376, a 94-run advantage.
West Indies' response was immediately halted as Woakes claimed skipper Kraigg Braithwaite for a duck in the first over.
Kirk McKenzie (eight) then fell to Gus Atkinson, while opener Mikyle Louis was fortunate to see Stokes drop a simple catch as the visitors reached stumps on 33-2.
Louis, on 18, and Alick Athanaze, on five, will resume batting on Sunday's third day with the Caribbean side 61 runs behind, and eight wickets intact to possibly make a fight of it.
Data Debrief: Root roars past Lara
Root delivered another impressive batting display for England. Although he was fortunate not to be dismissed in the second over, as replays showed he would have been given out had the Windies reviewed an lbw appeal.
Nevertheless, he fully capitalised with his 87 taking him past 12,000 Test runs, making him only the second England player to do so after Alastair Cook.
Although a 33rd Test century narrowly eluded him, Root did leapfrog Brian Lara into seventh place on the all-time leading Test run-scorers list.
Captain Kraigg Brathwaite leads the charge on the batting ranking, as he moved up two slots to 40th position, following scores of 48 and 47 in the second Test, which West Indies lost by 241 runs. They lost the first Test by an innings and 114 runs and will try to avoid a whitewash in the final Test in Edgbaston starting on Friday.
Wicketkeeper/batsman Joshua de Silva was rewarded for his first innings score of 82 in that match, as he jumped seven places to 61st, while Jason Holder’s 27 and 37 saw him inched up two places to 70th. Kavem Hodge’s 120, which was his maiden Test century, pushed him into the top 80.
The Dominican batsman moved 21 places up to 75th, one spot behind Kyle Mayers, who, despite being out of action, remains in 74th. Alick Athanaze held firm in 77th, while discarded Jermaine Blackwood (50th), Tagenarine Chanderpaul (83rd), Roston Chase (86th), and Kirk McKenzie (100) are the other Caribbean batsmen in the top 100.
On the bowling chart, new-ball bowlers Alzarri Joseph and Jayden Seales made the only notable improvements to their rankings. Joseph moved up two places to 33rd after finishing with five wickets in the match, and Seales moved up 10 places from 44th to 34th with six wickets.
Meanwhile, England batter Harry Brook has achieved a career-best third position after notching a century in the second Test.
Brook, who scored 36 and 109 in Nottingham, advanced four places, while his teammates Ben Duckett and Ollie Pope have also made significant gains in the latest weekly update to the men’s rankings, which are carried out on Wednesdays across formats.
Left-handed opener Duckett has progressed six places to 16th position after notching scores of 71 and 76, while Player of the Match Pope has advanced from 29th to 21st with scores of 121 and 51.
Chris Woakes is back into the top 20 of the bowling rankings for the first time since September 2021, after he finished with four for 84 and two for 28 in the match, while spinner Shoaib Bashir has advanced 18 slots to 53rd position after he took his third five-wicket haul in just his fifth Test.
In the ICC World Test Championship standings, England are placed in sixth place, while West Indies are ninth, as per the percentage points that determine qualification.
The tourists showed some fight as the day drew to a close before being bowled out for 236, but England's turn with the bat was cut short due to bad light.
Sri Lanka got off to the worst possible start as England ripped through them 6-3 in the first seven overs, with Woakes (3-32) getting a double-wicket maiden, dismissing Nishan Madushka and Angelo Mathews.
Shoaib Bashir (3-56) kept up the pace after lunch, as Sri Lanka slumped to 113-7, but they soon found their footing.
Captain Dhananjaya de Silva dug deep, racing to 74 off 84 balls, while Milan Rathnayake added 72 before Bashir dismissed them both. Stand-in captain Ollie Pope then ran out Vishwa Fernando to end Sri Lanka's innings.
With the light already poor, Sri Lanka were forced to open the bowling with spin - Ben Duckett and Dan Lawrence moved to 22-0 before the umpires intervened, leaving 12 overs unbowled.
Data Debrief: Pope makes strong start
Pope is the 82nd man to captain England in Test cricket, and the 12th this century. Despite losing the coin toss, he could not have asked for a better start after taking over from the injured Ben Stokes.
For Sri Lanka, Rathnayake impressed on his debut after helping to drag Sri Lanka towards the 200 mark - his tally of 72 is the highest score ever made by a number nine on Test debut.
