Webb has been out of the squad since injuring his foot against Italy in September, but played the full 80 minutes' in Ospreys' 19-16 defeat by Leinster at the weekend.
The 27-year-old met up with the rest of the squad on Monday ahead of the game in London and has returned after six months away from rugby.
Wales coach Warren Gatland was boosted by the news about Webb, he said: "It's great to have Rhys back in the squad. He has been training really hard and brings a lot of energy and experience to the team."
However, Gatland has named an unchanged side to the one that secured a 19-10 victory over France last time out, to ensure that Wales remain unbeaten in this years championship.
Gareth Davies will remain at scrum-half as Webb starts from the bench whilst lock Luke Chateris also takes a place on the bench, but Paul James comes in to cover injured Gethin Jenkins who suffered a calf strain against France.
Wales wary of England threat
Gatland understands the test that lie's ahead, but belives that the experience in the Wales side can still help them secure a six nations championship. He said: "We've named a pretty experienced side for Saturday."
Gatland explained that they have "a couple of guys back from injury on the bench" such as Charteris, James and Webb, which he called "a bonus." He also sid that there is "a huge amount to play for" on Sunday and suggested the game will go "a long way to deciding the Six Nations."
Both England and Wales are without defeat in this years tournament, but it is England who remain on course for both a grand slam and a triple crown.
Eddie Jones' men have beaten Scotland, Italy and Ireland already this year and a win over Wales would secure a second triple crown in as many years. Wales are too unbeaten but an opening 16-16 draw with Ireland in Dublin means they remain one point behind their opposition this weekend.
Wales Team: Liam Williams; Alex Cuthbert, Jonathan Davies, Jamie Roberts, George North; Dan Biggar, Gareth Davies; Rob Evans, Scott Baldwin, Samson Lee, Bradley Davies, Alun Wyn Jones, Dan Lydiate, Sam Warburton (capt), Taulupe Faletau.
Replacements: Ken Owens, Paul James, Tomas Francis, Luke Charteris, Justin Tipuric, Rhys Webb, Rhys Priestland, Gareth Anscombe.