Neymar scored his first goal for Barcelona as the Catalans came from behind to salvage a draw in the first leg of the Spanish Super Cup at the Vicente Calderon.
The Brazilian scored within seven minutes of coming on in the second half, cancelling out David Villa's spectacular opening goal against his former club, while Sergio Busquets was fortunate not to be sent off midway through the second half.
Barcelona produced a very different performance to their 7-0 thrashing of Levante at the weekend, and struggled to assert their authority in the first half.
They improved after the half-time break, with Cesc Fabregas replacing Lionel Messi, who had offered very little in the 45 minutes he was on the pitch. Fabregas' appearance sparked an improvement from the Catalans, but they were unable to grab a winner after Neymar levelled.
Atletico coach Diego Simeone had his tactics down to a tee in the first half, as his players stifled Barcelona, allowing them the ball but very little space.
Xavi Hernandez was anonymous, Messi looked suffocated by Atletico's pressing, while Andres Iniesta, the only player able to do something with the ball, had no-one to combine with. The visitors' only chances were a wayward shot from Messi from outside the area, and a deep cross from Dani Alves which Alexis Sanchez failed to get on the end of.
Atletico took the lead on 12 minutes through a stunning goal from former Barcelona man Villa, who joined Los Rojiblancos in the summer for 2.1million euros (£1.8 million), three years after the Catalans had paid Valencia 40million euros (£34 million) for him.
Simeone's side recovered the ball just beyond their own penalty area and made their way forward via a series of short passes, leading to Villa to release Arda Turan, who put in a first time cross from the byline towards the penalty spot, where Villa reappeared to meet the ball on the volley, sending it into the bottom corner.
The Spain striker then almost scored an even better goal as he tried his luck from the half-way line, but although the effort was beyond Barcelona goalkeeper Victor Valdes, it went just over the bar.
Messi was substituted at half-time, the second game in a row he has been taken off by Barcelona coach Gerardo Martino, and was replaced by Fabregas.
The former Arsenal man had an immediate impact, creating Barca's best chance so far within moments of coming on. He played in Alexis, who was thwarted by Atletico stopper Thibaut Courtois, and the ball came back to Fabregas, who was then tackled by Turan just as he was about to shoot.
Iniesta hit the loose ball at goal from 40 yards out, but Courtois saved it comfortably.
At the other end, Joao Miranda was inches away from getting on the end of a free-kick from Koke which would have resulted in Atleti doubling their lead.
Barcelona were lacking spark and Martino tried the obvious remedy - bringing on Neymar. The Brazilian replaced Pedro on 59 minutes and seven minutes later opened his account for the club that paid 57million euros (£48.7 million) for him. His compatriot Alves crossed from the right hand side and the 21-year-old appeared at the far post to nod in from just a few yards out.
Moments before the goal, referee Alberto Undiano Mallenco incensed the home crowd by refusing to give a second yellow card to Busquets for bringing down Villa to prevent Atleti breaking. He had earned a booking for an identical incident in the first half.
Once Barca equalised they looked more at home and pushed on for the winner.
They could have got one when Alexis arrived at the back post, but Courtois threw out his hand to deny the Chilean and force a corner.
At the other end, Villa had a shot on goal from a narrow angle, but Valdes was able to save comfortably.
Barcelona will be confident of their chances at winning the trophy next week in front of their own fans, but will need to produce a better performance than what they managed in the Spanish capital if they are to overcome Simeone's disciplined side.