Roy Hodgson's men have little margin for error with four matches left in Group H, and the Manchester City man believes they cannot afford to take anything for granted
Roy Hodgson's men triumphed 5-0 in the reverse fixture in Chisinau a year ago, but approach this fixture deprived of the likes of Wayne Rooney, Daniel Sturridge and Glen Johnson through injury.
And Milner believes it is crucial that England, who trail Montenegro in Group H by two points with a game in hand, are not complacent when they take on the minnows.
"It was a good performance out there in Moldova, we managed to get on top early so hopefully we can do that on Friday," he told reporters.
"We have a tough game on Friday first, but when we go out to Ukraine there will be a great atmosphere.
"We have four games left and it's in our hands. It's down to us to perform in them and finish the job."
With so many senior players absent, debutants Ross Barkley and Andros Townsend may get their chance to shine in a Three Lions shirt - and Milner is hoping they do.
"It's pleasing that we have some young players form the U21s stepping up. It shows there is the quality there," he added.
"It's a really good time to be in the England squad, we have a good mix of younger and older players.
"It doesn't take too much motivation to play for your country. Everyone is desperate to do their best for the Three Lions."