Neither goalkeeper was truly tested during normal time or the additional 30 minutes as a Nations League final went the distance for the first time, and two spot-kick saves by Unai Simon from Lovro Majer and Bruno Petkovic denied Zlatko Dalic's side an elusive international crown once again.
A few hours on from Italy's thrilling 3-2 success over the Netherlands in their third-placed playoff, the first half of Sunday's final was much more tame in comparison, with both sides probing but unable to make inroads.
The first real chance of the game came the way of Gavi in the 12th minute, as Spain suffocated Croatia with their high press and presented the Barcelona starlet with the chance to let fly from 20 yards, but his shot trickled just wide of the far post.
Croatia were unable to expose Spain's high line, but the Chequered Ones tried to take the game by the scruff of the neck as the half drew to a close, led by conductor Luka Modric.
The Real Madrid man sent in a deep delivery to the back post with 39 minutes gone, which Ivan Perisic got on the end of, but his header was meat and drink for Simon.
Alvaro Morata rose highest to meet a Jordi Alba cross just three minutes later, but he nodded harmlessly over the bar before La Roja made a meal of a free-kick routine on the stroke of half time.
That wasted chance denied Spain their first shot on target before the break, but Croatia right-back Josip Juranovic also left his shooting boots in the dressing room, as he flashed a cross-cum-shot across the face of goal from just outside the six-yard box in the 51st minute.
The end-to-end action soon resumed, as Alba once again sent in an inviting ball from the left in the 57th minute, and this time it was Marco Asensio's turn to head over Dominik Livakovic's goal.
In desperate need of a moment of magic, Rodri tried to provide it for La Roja with 65 minutes gone, but the Manchester City man's fierce effort from distance flew wide of the post.
The introductions of Barcelona's Ansu Fati and soon-to-be Real Madrid attacker Joselu sparked some life into the Spain attack, and the former finally notched La Roja's first shot on target in the 84th minute, but his goal-bound strike from inside the box was cleared off the line by Perisic.
Extra time subsequently loomed, and clear-cut chances remained at a premium as legs began to tire, but Nacho Fernandez was required to make a terrific last-ditch tackle to prevent Majer breaking the deadlock with 100 minutes on the board.
There was some concern for Spain when Nacho stayed down, as Luis de la Fuente had already used up his allocated substitutions, but the Real Madrid captain was fine to continue for the second period of extra time.
Spain piled on the pressure in the final 15 minutes, but spot kicks would ultimately be needed to separate the two nations, as Croatia sought to win their fifth shootout in a row, while Spain were out to end a run of three successive penalty-decider defeats.
Following a brief fracas between the two benches - tension from extra time perhaps spilling over - the nations stepped up to the spot, where the feet of Simon denied Majer after six perfect penalties.
Asensio and Perisic subsequently made no mistake, leaving Aymeric Laporte with the chance to seal glory for La Roja, but the Manchester City man crashed his effort off the bar to spark sudden death.
However, Laporte was the most relieved man in the stadium when Simon repeated his heroics against Petkovic, and Dani Carvajal lifted one final sumptuous penalty beyond the reach of Livakovic to break Croatian hearts again.