The task of taking on Jose Mourinho's men away has been notoriously difficult, with the London outfit suffering only one home defeat this season and none in the Premier League at all in either of the Portuguese's spells in charge.
They did, however, suffer a dramatic 3-2 league loss at Stoke last month - something Hughes is optimistic may count in his team's favour with regard to psychology this weekend.
The Welshman, a former Chelsea player, said: "We take confidence from the fact that we have already beaten them this season.
"It wasn't at Stamford Bridge and, historically, Stamford Bridge when Chelsea are under Mourinho has been a very difficult place to get a positive result.
"But the fact that we have beaten them I think will help us - and possibly play on their minds somewhat.
"We have to try to use that to our advantage.
"There won't be any apprehension in terms of what we are going to try to do.
"If we do it well, on our day we are difficult for anyone, as we have proved - and as Chelsea know."
After the Chelsea game, Stoke - currently 14th in the Premier League and only four points clear of the relegation zone - have a top-flight fixture at Sunderland on Wednesday.
Hughes admits he will be mindful of the trip to the Stadium of Light when he makes his team selection for Sunday's match, but has also stressed that he feels it is possible for him to "go strong" for the cup tie and that it is a case of "getting the balance right".
When it was put to him that Stoke fans might deem the Sunderland encounter more important than the Chelsea one, Hughes said: "I can understand that.
"I think Premier League points are vitally important to us.
"But we are playing Sunday and then Wednesday and I feel, if I want to go strong, I can do because of the time-scale involved - obviously it would have been different if we had been playing Sunday and then Tuesday.
"The extra day gives us time to recover, so we will see.
"I think there is an opportunity to go as strong as I would like, but it is about getting the balance right as well and I am mindful of the game on Wednesday."
Stoke goalkeeper Asmir Begovic could make his return to action on Sunday after being sidelined for six matches by a broken finger.
Kenwyne Jones, who was not considered for selection last time out as a result of his refusal to play in the game before that, may also be back in the squad, with Hughes having said the striker ''comes into our thinking''.
John Guidetti, the frontman on loan from Manchester City, will be assessed having felt ill on Friday, while Robert Huth (knee), Andy Wilkinson (heel) and Matthew Etherington (calf) remain unavailable.
Winger Jermaine Pennant will not feature as he has been released by the Potters.