Spain came back from 2-0 down to draw 2-2 with Colombia before winning 4-2 on penalties in Saturday's Olympic quarter-final.
La Roja went into the clash in Lyon having enjoyed a perfect record at the Paris Games, but were on the brink of a shock exit when Leicy Santos put Colombia 2-0 up.
Santos' goal came after Mayra Ramirez had opened the scoring for Colombia at the Groupama Stadium.
Yet Spain fought back late on, with Jenni Hermoso scoring in the 79th minute before captain Irene Paredes netted deep into injury time.
Extra time came and went, and Cata Coll proved Spain's hero with a save from Catalina Usme, while Colombia substitute Liana Salazar also missed the target.
That paved the way for Aitana Bonmati, the Ballon d'Or winner, to dispatch the winning spot-kick and tee up a meeting with France or Brazil in the last four.
Data Debrief: Spain's quality inspires fightback
Despite creating fewer expected goals (xG) than their opponents, with 1.05 to Spain’s 2.52, Colombia showed real effectiveness in taking the chances that were presented to them.
They scored close-range goals from just four shots inside the area and seven in total, while they only had eight touches in the opposition box for the entirety of the 120+ minutes.
But Spain overwhelmed Colombia as the match wore on, as evidenced by a huge gulf when it came to final third entries, with 155 for La Roja to 26 for their opponents, while they also enjoyed 46 more touches in the opposition box than their opponents.
Paredes was ultimately Spain's hero in regulation time. She has been involved in three goals in her last five games for her country (two goals and one assist), the same as in her previous 30 games in all competitions (two goals and one assist).
Brazil 4-2 Spain: Selecao through to Olympics final with resounding win
Brazil cruised into the final of the Olympic Games with a 4-2 victory over Spain at the Orange Velodrome on Tuesday.
Salma Paralluelo netted two late consolations, but the damage was already done as Irena Paredes' own goal, Gabi Portilho, Adriana and Kerolin denied the world champions a place in the gold-medal match.
Brazil were still without legend Marta after she lost her appeal over a two-game ban, but her team-mates ensured she would bow out of Olympics action with the chance to play for the top prize.
Spain were behind after just six minutes as Cata Coll's poor clearance struck the unfortunate Paredes on the side to send it cannoning over the line.
La Roja struggled to gain a foothold, and Brazil doubled their advantage on the stroke of half-time thanks to Portilho's composure when one-on-one with Coll.
Adriana made sure of their progress off the bench in the 71st minute – she struck the bar but was then on hand to head Portilho's nod-down in from close range.
That sparked Spain into life and Paralluelo's looping header snuck in at the far post before Alexia Putellas rattled the crossbar and forced Lorena into a smart stop to slow down the comeback attempts.
Kerolin delivered the hammer blow in the opening seconds of stoppage time by sliding her low shot through Coll's legs, though Paralluelo would have the last say, poking in her second of the match from close range in the 112th minute.
Data Debrief: World champions denied
Spain were aiming to become the first side to win Olympic gold after lifting the Women's World Cup, but they just fell short at the final hurdle after being outplayed.
La Roja's late flurry of chances meant they finished with more shots than Brazil (26 to their 17) and more on target (11 compared to seven).
Brazil's dominance showed in other ways though, as they created an expected goals (xG) of 3.27 and had a total of six big chances, as they secured a meeting with the United States in the final on Saturday.
St. Lucia’s Alfred adds 200m silver to 100m gold; USA’s Thomas claims first Olympic title
St. Lucia’s Olympic 100m champion Julien Alfred continued her brilliant showing at the Paris Games with silver in the final of the Women’s 200m at the Stade de France on Monday.
The 23-year-old recovered from a less than ideal start with a strong finish to cross the line second in 22.08.
Gold went to American Gabby Thomas who ran 21.82 while another American, Brittany Brown, took bronze in 22.20.
Great Britain’s Dina Asher-Smith and Daryll Neita ran 22.22 and 22.23, respectively for fourth and fifth while Nigeria’s Favour Ofili ran 22.24 in sixth.
American McKenzie Long (22.42) and Ivory Coast’s Jessika Gbai (22.70) rounded out the top eight.
Dynamo Kyiv 1-1 Rangers: Dessers leaves it late to salvage first-leg draw
Cyriel Dessers salvaged a last-gasp draw for Rangers in a 1-1 draw with Dynamo Kyiv in their Champions League third-round qualifier first leg on Tuesday.
It looked like Andriy Yarmolenko's strike would give the Ukrainian side the advantage heading into the second leg next week, but the visitors dug deep to level the score.
Rangers made a decent start to the game but were punished for Ridvan Yilmaz's loose pass, as Vladyslav Vanat capitalised by flashing it into the box for Yarmolenko to turn home.
The visitors pushed for an equaliser, with Ross McCausland hitting the post before Heorhiy Bushchan made a fine save to keep out Dessers' pacey shot.
And it was the Nigerian that eventually found the breakthrough for Rangers as he darted in to poke Vaclav Cerny's cross past Bushchan with the last kick of the game in the 94th minute.
Data Debrief: Dessers saves the day
For so long, it looked like Rangers would be heading back to Hampden Park next Tuesday with a deficit to overturn, but Dessers' threat finally paid off.
Philippe Clement's side have started the season with back-to-back draws though, having played a 0-0 stalemate with Hearts in the Scottish Premiership at the weekend, and he will be keen to get their first win soon.
Although Dynamo could not hold out for the win, they are now unbeaten in their last 12 home matches in all competitions, winning 10 and drawing two.
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