The Chelsea left-back will be 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).
Hodgson said: "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."
It has been a testing week's preparation for the England camp with a number of withdrawals, including strikers Jermain Defoe and Daniel Sturridge, as well as midfielder Michael Carrick.
But Hodgson remained upbeat on his available squad, adding on Tuesday: "Everybody is fit. We were disappointed to lose the three players we originally selected but luckily we've still go plenty left.
"We all trained today and we're all now set for tomorrow."
Hodgson did rule out the possibility of Cole leading the side out at Wembley in place of captain Steven Gerrard, who made his 100th appearance for England in last November's friendly with Sweden.
"I don't see any reason why the captain should let anyone else lead the team out," he added.
"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."
Hodgson conceded Cole is under more pressure for his place than at any time in his 11-year international career from Everton left-back Leighton Baines.
He said: "Cole is playing well and Leighton is also playing well. I'm pleased to have the headache. It won't be an easy choice when they are both fit and vying to play in the important games."
Regarding tactics for the showdown with the five-time World Cup winners, Hodgson admitted Theo Walcott was an option to play up front due to injuries to Defoe and Sturridge, but stressed major experimentations were not on the agenda.
"We're taking the game too seriously for me to even entertain the word experiment," he said.
"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."