The French midfielder shared a picture of himself looking smug with the line: "Caption this!", just minutes after the Portuguese was given his marching orders.
It led to a a furious response from United legend Gary Neville who demanded Pogba should follow Mourinho out of the Old Trafford exit.
Pogba's sponsors Adidas insisted the player had not aimed the smirking pic in an effort to taunt Mourinho – with the pair having endured a fractious relationship for the past year.
They insisted it was a pre-scheduled Instagram post as part of his commercial deal following a photo-shoot in Italy earlier this week.
But despite being deleted ten minutes after it was published, the damage was done with over 64,000 individual likes and huge attention globally as a result of Neville's response.
Mourinho and Pogba fell out and this was one of the reasons for the Portuguese's downfall
And the Mail say the issue has been viewed dimly by bosses at United, who believe it was "disrespectful" no matter whether it was intended.
They are understood to believe it was in bad taste given the circumstances and are ready to come down hard.
The £300,000-a-week star is set to be spoken to and hit with a club fine, with United believing he and his commercial team should have been more aware of the situation.
One Adidas spokesman said: "Pogba's social media posts were a scheduled event, part of a marketing campaign.
"Immediately taken down once it became apparent that it could be misconstrued as disrespectful to Manchester United and Jose Mourinho".
Mourinho was shown the door after guiding the Red Devils to their worst start to a league season in 28 years.
And his fractious relations with flamboyant midfielder Pogba has ultimately been a crucial factor to his downfall.
The pair had an infamous training ground bust-up in a video which went viral on social media.
The former Chelsea chief also made an astonishing attack on his record signing earlier this month – labelling Man Utd's record signing 'a virus' in front of his team-mates.
Red Devil legend Neville also gave his reaction to Mourinho's sacking on Sky Sports.
He said: "The management team have had three chances of recruiting a manager, they are probably going to get their fourth and my personal view – and I've said this for some time – the club needs to reset.
“This is a moment for the club to take stock of what they are doing and reset the structure in terms of recruitment and the decision-making at the football club and make sure what they do next is the right move.
“It's not about speed, it's not about rushing and getting the first manager that's available, it's about making sure the next manager is the right manager.
“They will have to pay for him if it's the one we think it's going to be (Mauricio Pochettino). They have to make sure they put the right structure in around him.
“They see it as a positive that they have 65 scouts, I see it as confusion. Especially if you don't have a definitive person with a level of control.
“They've got to put more intelligent people in there who understand the football side of things.”
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