Jones is one of four "captains" in Hansen's squad, but incumbent skipper Martyn Williams was expected to retain the job. Jones is Wales' 120th captain and the country's eighth skipper since 2000.
"The match offers us an opportunity to grow Stephen's leadership on the field and it gives Martyn a bit of a break," said Hansen.
"The selection has no bearing on the captaincy selections during the World Cup."
Hansen said the England team had a powerful pack and pace out wide, but "we have the talent to give this game a good crack".
"It's clearly not the best England team, but it's far from a weak side. A lot of their players are after a seat on the plane to Australia and that makes them very dangerous."
Jones said the captaincy was a "great honour", but didn't expect to retain the position for the Cup in Australia.
"You'd have to say Martyn is in the pole position for the World Cup, but I can't wait to lead the team out at the Millennium Stadium.
"England is a huge match and we're showing them the greatest respect."
The Wales starting lineup is as expected, with New Zealand-born centre Sonny Parker returning from injury and veteran winger Gareth Thomas being the only player from the starting lineup who lost 12-35 to Ireland last Saturday to retain his place.
Centre Mark Taylor added: "We did quite well in the Six Nations against England (losing 9-26). Now we've got them in Cardiff again and supposedly with their second-string side so I guess it's our best chance to beat them since 1999.
"We just need to start winning again. We've got an experienced side and they've got a few new caps in theirs. This is a chance for us."
Hooker Robin McBryde is expecting a no-holds-barred encounter.
"It certainly isn't going to be a friendly. Everybody wants to get on the plane to Australia so there's plenty to play for. There's pressure on everyone in all positions - nobody can relax.
"Any team that England puts on the field these days is a good one - just look at their front row. They rotate their squad very well, and just look at the experience they've got in their pack.
"It shouldn't take that long for us to knit together. We've just come back from a summer tour and we've been training together for almost six weeks."
Teams (kick-off 2.30pm)
Wales: Rhys Williams (Cardiff Blues); Mark Jones (Llanelli Scarlets), Mark Taylor (Llanelli Scarlets), Sonny Parker (Celtic Warriors), Gareth Thomas (Celtic Warriors); Stephen Jones (Llanelli Scarlets, captain), Gareth Cooper (Celtic Warriors); Iestyn Thomas (Llanelli Scarlets), Robin McBryde (Llanelli Scarlets), Gethin Jenkins (Celtic Warriors), Rob Sidoli (Celtic Warriors), Chris Wyatt (Llanelli Scarlets), Colin Charvis (unattached), Martyn Williams (Cardiff Blues), Dafydd Jones (Llanelli Scarlets).
Replacements: Gareth Williams (Cardiff Blues), Adam Jones (Neath-Swansea Ospreys), Jonathan Thomas (Neath-Swansea Ospreys), Gavin Thomas (Neath-Swansea Ospreys), Mike Phillips (Llanelli Scarlets), Gavin Henson (Neath-Swansea Ospreys), Tom Shanklin (Cardiff Blues).
England: Dan Scarborough (Leeds Tykes); James Simpson-Daniel (Gloucester), Jamie Noon (Newcastle Falcons), Stuart Abbott (London Wasps), Dan Luger (Perpignan); Alex King (London Wasps), Andy Gomarsall (Gloucester); Jason Leonard (NEC Harlequins, captain), Mark Regan (Leeds Tykes), Julian White (Leicester Tigers), Danny Grewcock (Bath), Simon Shaw (London Wasps), Martin Corry (Leicester Tigers), Lewis Moody (Leicester Tigers), Joe Worsley (London Wasps).
Replacements: To be announced.