Philippe Coutinho opened the scoring in the second minute after Hugo Lloris made a rash decision by coming off his line as Barcelona have dominated throughout at Wembley.
It was a testament to Tottenham's character that they twice scored goals through Harry Kane and Erik Lamela to give themselves hope of an unlikely draw, but Barca were always deservedly one step ahead.
Pochettino pointed to that mistake as the key component to why Barcelona were able to dictate the game and get Messi into plenty of space. I say it honestly, not because he plays on my team.
'It was a very hard game tonight, they have top players up front, they moved the ball a lot and we ran a lot during the first half.
Messi has made a strong start to the season with 10 goals in all competitions, including five in LaLiga and as many in the Champions League. He has five goals in two UCL games this season, at a rate of one goal every 36 minutes. "It's an honour to play alongside him".
In recent weeks there have been murmurs that Barcelona have been struggling after three games without a win in La Liga. His floated pass was chested down by Luis Suarez to Coutinho whose volley sliced up in the air before the quick-thinking Brazilian hooked the ball back to Rakitic who rifled a picture-perfect right-foot volley in off the post from 25 yards.
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Barcelona were vulnerable so they said, but on a pitch scarred from hosting British heavyweight champion Anthony Joshua's fight against Alexander Povetkin they took only two minutes to catch Spurs in the solar plexus.
A great start for Barcelona, what Lloris had in mind will remain a mystery.
Rakitic stole the spotlight midway through the first half when the Croatia midfielder struck with a thunderous half-volley. But what the scoreline did do was set the stage for a pulsating second-half.
Considering his well-earned reputation as one of the world's most feared strikers, it is nearly inexplicable that Luis Suarez has now gone more than three years without an away goal in the Champions League.
Spurs twice rallied, making it 2-1 and then 3-2 and almost equalising with a deflected Lucas Moura effort, but Lionel Messi's 90th-minute strike - his second goal of the night - ended Spurs' hopes. Previously reliable, Lloris errors are now far too regular.