Kansas last won the National Championship in 2008, finishing runners-up in 2012 and making the Final Four again in 2018, while it was North Carolina's fourth title game appearance since 2008, winning titles in 2009 and 2017 and finishing runners-up in 2016.
Despite being considered two of college basketball's premier programs, Kansas was the much better side this season, entering March Madness as a one seed while North Carolina was an eight seed.
However, the Tar Heels were not interested in the script, and after a back-and-forth start, the first half belonged to North Carolina as cult hero Brady Manek splashed three triples on the way to a 40-25 half-time advantage.
But the Jayhawks had faced adversity earlier in the tournament and stuck to the task, storming back to begin the second half as Christian Braun and Jalen Wilson ignited a 20-6 Kansas run to pull the margin back to one at 46-45.
Remy Martin was a crucial spark off the bench for Kansas, chipping in with 14 points on five-of-nine shooting, but it was center David McCormack who rose to the occasion down the stretch.
Trailing 68-69 with less than 90 seconds to play, McCormack hit two consecutive contested hook-shots out of the post to deliver the final winning margin.
Baylor, which boasts two likely first round picks in this year's NBA draft in Jeremy Sochan and Kendall Brown, looked dead in the water with 10 minutes to play, trailing 67-42.
From that point on it was like a scene from a movie, as the Bears could not miss, while the Tar Heels committed silly mistakes as the pressure mounted.
Trailing by six points with 35 seconds on the clock, Baylor's Sochan hit a three, before North Carolina missed both free throws, allowing James Akinjo to tie the game with a three-point play to force overtime.
Against all momentum, North Carolina steadied in the overtime period, winning it 13-6 to ultimately prevail 93-86.
The Peacocks thrived off a home-court advantage at the Wells Fargo Center to become the first 15th seed to reach the Elite Eight, despite the late efforts of NBA lottery prospect Jaden Ivey.
Despite hitting on none of his opening five attempts from the perimeter, Ivey connected on an NBA-range triple with eight seconds left to bring Purdue within a point. Doug Edert calmly made his free-throws to ice the game, and put Saint Peter's on the brink of the Final Four.
They will face North Carolina who defeated UCLA 73-66, led by 30 points from Caleb Love.
Despite shooting 10-of-31 from the three-point line for the night, the six-time national champions overcame a three-point deficit to put up 45 points in the second half.
Elsewhere, Remy Martin scored a season-high 23 points as Kansas hung on for a 66-61 win over Providence, securing their passage to the Elite Eight.
The Jayhawks are the only first seed left in the tournament, after both Gonzaga and Arizona were defeated in the Sweet 16 on Thursday, and Baylor's title defence was ended in the second round.
Kansas will face the Miami Hurricanes, who progressed with their comfortable 70-56 win over Iowa State.