Arsenal claimed victory in the traditional curtain-raiser of the Premier League season in dramatic circumstances.
Leandro Trossard's equaliser in the 11th minute of stoppage-time cancelled out Cole Palmer's excellent opener to send the match to penalties.
And after City duo Kevin de Bruyne and Rodri couldn't convert their spot-kicks, Fabio Vieira was the hero for the Gunners when he dispatched an expert penalty to see Arsenal win 4-1 in the shootout.
In the ITV studio, Pougatch was joined by Keane and Chelsea Women's boss Emma Hayes as they dissected the action.
And as the coverage came to an end, Pougatch signed off by saying: "Vieira wins it from the spot against a Manchester team, we've heard that before!
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"What's it going to mean? We'll find out, goodbye."
It was at this point that Keane darted a cold stare towards the ITV presenter in classic Keane fashion.
Pougatch was referring to the 2005 FA Cup final where Arsenal triumphed over Manchester United on penalties.
Keane captained the Red Devils with his nemesis Patrick Vieira his opposite number on the day.
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And Vieira was the difference-maker that day when he scored the winning penalty in the resulting shootout following a 0-0 draw.
It meant that the Gunners became the first side to win the FA Cup via a penalty shootout even though United had outplayed their adversaries on the day.
So it is no surprise that the result might rankle for Keane, despite having four FA Cups to his name by then.
That one might even sting a little harder, considering that was the last FA Cup final that the Irishman would appear in.
Nevertheless, on Sunday's evidence, Arsenal are readying themselves for another title surge after coming close last season.
City's relentless form meant that they leapfrogged the Gunners late into the campaign, as they claimed an incredible treble.
But claiming silverware over them at Wembley will give Mikel Arteta's men a major confidence boost.