A club statement said the full extent of the injury is not yet known but the Belgium worldwide was undergoing tests.
It's a huge blow to Pep Guardiola's side, with De Bruyne the key man behind their title win last season.
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The Belgian midfielder is understood to have sustained a knee injury during training on Wednesday and could be out of action for anywhere between two and three months.
Sam Lee from Goal has since reported that the Belgian worldwide is already on crutches from the training ground and will be assessed in both Manchester and Barcelona.
Speaking at the premiere, Walker said: "Kevin is a great player and it's just unfortunate that it's happened to him in training but there's more than enough depth in the squad".
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'It is unlucky for Kevin - the season has only just begun and it's always good to be back but as long as his ligaments are not torn we can remain hopeful he'll make a quick recovery'.
Any team in the world would miss a player of De Bruyne's quality.
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City are well-stocked in the midfield positions, with Ilkay Gundogan, David and Bernardo Silva as well as the emergence of exciting 17-year old Phil Foden. He was maybe the main man for us last season.