The winger joined the Potters three years ago from Real Zaragoza, initially on loan, but made only two appearances for the club last season, both in August.
He was sent out on loan to Wolves by then Stoke manager Tony Pulis and was frozen out of the first-team picture when he returned in January.
Pennant was released by the club when his contract ended, but Pulis was replaced in the hotseat by Hughes in May and the Welshman offered the player a one-year deal to stay.
He accepted and Hughes sees no reason why he cannot be a real asset for Stoke.
"He's been given another opportunity here," said the Potters boss.
"He loves the club, he didn't want to leave. He thought possibly he would have to but things change very quickly in football and he's got another chance.
"I'm sure he'll take it because he's a good guy and he works hard. I think people sometimes get the wrong impression of Jermaine but he wants to play football and he wants to make an impression for us."
Pennant was unable to travel with Stoke for their pre-season tour of the US because of his criminal record but looked lively in his first outing against Wrexham yesterday.
Hughes said: "Unfortunately we couldn't take him to America, everybody understands the circumstances, but he's been with the under-21s and he's been first class.
"Glyn Hodges gave him a glowing report in terms of his attitude to the games he's played and being in and around the under-21 guys. I was really pleased to hear that."
Another player who looks likely to benefit from Hughes' appointment is midfielder Wilson Palacios.
The Honduras international joined Stoke two years ago but has started only 18 games in all competitions in that time.
Palacios has been linked with a move to Premier League newcomers Hull, but has been very involved in Hughes' pre-season plans and played 45 minutes of yesterday's 1-0 friendly win over Wrexham.
Hughes said: "He hasn't really surprised me because my view was always that Wilson was a very good player and I was pleased he was still in the building.
"Obviously he's had a difficult time for whatever reason but he's an accomplished player, a good international player who understands the role. He's certainly in my thoughts."
Stoke begin their Premier League campaign against Liverpool at Anfield a week on Saturday.