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Gareth Southgate's side ran out comfortable winners on Saturday evening to set up a huge semi-final clash with Denmark on Wednesday.
The Ukraine clash was England's first game away from Wembley and it took place at the Stadio Olimpico - home of Serie A side Roma.
Mourinho is set to become Roma manager next season and he famously doesn't get on well with Shaw, who he managed for two years at Manchester United.
The 25-year-old provided assists for Harry Kane and Harry Maguire and was asked if his performance was extra special on Mourinho's new stomping grounds.
He replied after letting out a chuckle: "Look, it doesn't matter I think Jose has his opinion, he's obviously working for talkSPORT and it's freedom of speech, he can say what he likes.
"He can say whatever he likes, I just keep my head down, ignore everything. My main objective is to help England."- beIN SPORTS (@beINSPORTS_EN) July 3, 2021
Who is Luke Shaw talking about? #beINEURO2020 #EURO2020 #UKRENG
Watch Now - https://t.co/RRmQgctETJ pic.twitter.com/z7yYFH9UJY
"I just keep going and keep my head down. I ignore everything and focus on what's going on inside the camp... my objective is to help England and no matter what, I'll keep on giving everything."
At around the same time, Mourinho appeared on talkSPORT and said, "Luke Shaw is playing better and better," unaware of his former player's comments.
Fans noticed Shaw's reaction and they're loving that he's finally getting the last laugh.
Luke not recognising the Muppet getting the Roma job has made my day:joy: https://t.co/nNgiFrr8Q4
- Sam (@sjhphoto1) July 3, 2021
The fact that Shaw doesn't give a damn must hurt Jose so much :sob: https://t.co/Tf85lLCFiF
- CamTLR (@CamNiz) July 3, 2021
Shaw's assist for Maguire came from a free-kick, which is ironic given Mourinho's criticism last month.
Speaking on talkSPORT, the Portuguese coach called Shaw's set piece delivery 'dramatically bad' during the Czech Republic game.
He explained: "The negative thing I would say is once more they were very poor on attacking corners.
"The service was dramatically bad. They have so many good players to attack corners. The crosses are not passing the first man.
"Luke Shaw, in my opinion, very good tonight but very poor on the corner. [Kalvin] Phillips, the same.
"England has great power at this level and going to knockouts, one corner can decide a game."
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