The Chelsea left-back will become the seventh player to make 100 England appearances, following in the footsteps of Peter Shilton (125), David Beckham (115), Bobby Moore (108), Bobby Charlton (106), Billy Wright (105) and Steven Gerrard (100).
Asked if Cole would start, Hodgson told reporters: "Yes he will. He'll start the game, then I'll have to see what to do with Leighton (Baines), who has been doing very well. Ashley will definitely start."
Hodgson did, however, rule out the possibility of Cole leading the side out at Wembley on Wednesday in place of captain Gerrard, who made his 100th appearance for England in last November's friendly with Sweden.
Hodgson said: "I don't see any reason why the captain should let anyone else lead the team out.
"Ashley does his talking and work on the field and I don't think he's ever pushed himself forward during his 100 appearances as a potential captain of the team.
"I think he's just very happy to be a key player in the team so I'm pretty certain he won't be trying to rip the armband off Steven tomorrow.
As Cole prepares to join national captain Gerrard among England's centurions, the Liverpool man agreed his team-mate should now be mentioned as an all-time great.
"I think he deserves to be in there," he told Sky Sports News. "I look at the players I played with throughout my career and I think he's been one of the most consistent."
Despite the fanfare of a game organised to mark the FA's 150th anniversary, Wednesday serves mainly as a warm-up to two important World Cup qualifiers against San Marino and Montenegro.
Gerrard added: "Its exciting times and I think the FA have produced some fantastic fixtures.
"We start against Brazil and I know it's a friendly but we want to go into the qualifiers in good shape."
The Liverpool midfielder backed his Arsenal contemporary Jack Wilshere to establish himself for England after missing almost a year of football due to injury.
He added: "I think if he stays fit he's got the talent and the ability to be a top player for Arsenal and for England.
"He's had a disappointing time with injuries and I've been there myself. I hope he can get a good run in the team."
Gerrard also revealed his England team-mates have approached the FA with a view to supporting Paul Gascoigne after the former Three Lions midfielder admitted himself to a rehabilitation centre in the USA this week due to personal issues.
"It is something that we've already tried to do," Gerrard added. "We've spoken to the FA and we've made it clear we are able to help if needed."
On Gascoigne, Hodgson said: "He has our full support, our full morale support and anything we can possibly do to help him we'll be more than happy to do.
"I think it's a question for Paul now to get the treatment he needs.
"Kind words won't be enough, he needs some quite severe action and let's hope he gets what's required in order for him to pull out of this situation and come out on the other side as the player and person we all remember."
Looking ahead to Wednesday's match, Hodgson admitted Theo Walcott was an option to play up front due to injuries to strike duo Jermain Defoe and Daniel Sturridge.
However, the England boss insisted he was not looking to use the visit of Brazil as a chance for major experimentation.
"It (experimenting) is not a word I really want to use. We're taking the game too seriously for me to even entertain the word experiment, but on the other hand it is a friendly match, and you don't get to Brazil 2014 and take part in a World Cup by taking part in friendly matches even if you get great results against the top nations.
"For us, it's another important step along the way.
"We think it's a great way to start 2013 and our 150th anniversary, and we'll be doing our best to play well and get a good result, but finally for me it's a question of knowing by March what our best team is and what players play best together."
On the fitness front, Hodgson added: "We're disappointed to lose the three players who were originally selected, but luckily we've still got plenty left and everyone's trained today so we're all set for tomorrow."
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