Croatian goalkeeper Dominik Livakovic had a heck of a game as Brazil had to exit from the quarter-finals for a second successive time, against their European counterparts, losing 4-2 in the shootout in Doha Friday.
The five-time World Cup winners are yet to win any knockout fixtures against European sides since their last triumph in the biggest stage – in 2002 beating Germany in the final.
The match was closely fought and balanced at 0-0 ate the end of regular 90 minutes and forwarded to extra time after some heroics from Croatian goalkeeper, keeping Neymar and Co at bay at the fully-packed Education City Stadium.
But Brazil took the lead on the eve of half time of the extra period thanks to a wonderful goal by their star Neymar, but eventually the Selecao failed to keep the advantage as Bruno Petkovic restored the balance for Croatia in the 116th minute to take the game further.
Murquinhos missed from the spot as he hit the post and gave early advantage to Croatia, while Luka Modric and his men scored all the penalties and didn't give any chance to Brazil to come back.
Moreover, Livakovic denied Rodrygo Goes to give the floor to Nikola Vlasic, who then converted their fourth to take Croatia to another semi-final.
The result meant the dream semi-final fixture between Brazil and Argentina is now invalid, with the latter now taking on the Netherlands at Lusail Stadium just 22kilometers away.
Croatia were stubborn from the start of the game to frustrate Brazil, but the World Cup experts somehow got the flow with time and prevailed at the very end.
Brazil put out the same XI they played against South Korea in the last-16 tie, as first-choice left-back Alex Sandro didn't recover from a hip injury and stayed on the bench.
Croatia, on the other hand, made two changes in the starting line-up that won against Japan.
Borna Sosa returned from illness to replace Borna Barisic, while midfielder Mario Pasalic was introduced instead of forward Petkovic.
The Croats, wearing distinctive red-and-white checkerboard tops, started the game brighter of the two sides with continuous pressing, and didn't give the Men in Yellow enough scope to flourish with their rhythmic play.
In the third minute, last edition's runners-up showed some early signs that they are here to fight toe to toe when Mateo Kovacic on the left side dribbled and deceived Casemiro to earn a free kick that saw the ball enter the box at Marcelo Brozovic, who failed to make the most of the opportunity.
Croatia again went close to scoring in the 12th minute when Pasalic went down to the right flank to provide a dangerous low cross through six-yard box, which was missed by a whisker initially by Josip Juranovic then a couple of meters away by Ivan Perisic in front of a nearly-open goalpost, thanks to some close marking by the Brail defenders.
Selecao forwards Neymar, Richarlison and Vinicius Junior were failing to carry on their natural passing game as Croatian midfield, led admirably by Luka Modric, clearly had done their homework.
Vinicius provided Brazil their best move in the 20th minute.
Rushing in from the left wing, the Real Madrid man exchanged a pass with Richarlison and aimed a curler towards the bottom left that was blocked by Dejan Lovren, followed by a Neymar shot ending straight at the hands of Dominik Livakovic.
The players went to the tunnel with the score locked at 0-0 after the first half, and the game was evenly balanced.
Brazil after the break came to the field in refreshing mood and showed some difference in tactics with instant impacts, attacking heavily in front of the Croatian post.
In the 48th minute, Croatian defender Josko Gvardiol blocked from point blank range to frustrate Neymar after some fine work by Vinicius on the left side.
Seven minutes later, getting the ball after an elegant run by Richarlison down inside-left channel, Neymar glided to the left-hand corner but couldn't go past Livakovic, who again saved Croatia brilliantly from a one-on-one chance when Lucas Paqueta in the 66th minute got the ball open and free, resulting from a misunderstanding among a couple of Croatian defenders.
Ten minutes later, Neymar again failed at the hands of the Dinamo Zagreb goalkeeper when freshly-introduced Rodrygo Goes and Richarlison combined to release the ball to their No 10 down the inside-left channel.
Antony, replacing Raphinha, troubled the Croats' defence with his pace and sent a ball to his Manchester United clubmate Casemiro in the 80th minute.
But his cross found Rodrygo who then cut back for Paqueta, but Livakovic was on hand to deny him again.
After another goalless half, the game went into extra time and Brazil started the phase the way they finished the stipulated time; attacking on the final third.
Croatia captain Modric showed some wonderful skills in the eighth minute of extra time when the 37-year old nutmegged Guilherme Pedro out on the right.
Three minutes later, Pedro attempted a spectacular overhead kick, only to be thwarted by Livakovic.
And then at the very end of the half time of the extra period, Neymar gave the Selecao the moment of sheer joy after exchanging passes with Rodrygo and Pedro, then beating Livakovic on the right from a tight angle.
But Brazil weren't able to hold onto the lead as Mislav Orsic, with the help of Modric in the left side found Petkovic in the box.
Petkovic took the shot first time, and a slight deflection from Marquinhos took it past the diving Alisson Becker, sparking Croatian celebrations.