The Manchester United skipper will likely lead the line for Roy Hodgson's side in their final Group E qualifier of 2014 and become the ninth England player to reach the century mark in doing so.
Joining the likes of former international team-mates Steven Gerrard, Frank Lampard, Ashley Cole and David Beckham, Rooney will hope to mark his achievement with a fourth victory of the qualifying campaign.
England have been impressive in qualification for the European Championships after a dismal showing at the World Cup in Brazil, and boast an unblemished record ahead of Saturday's clash with second-placed Slovenia.
Sreko Katanec's side have lost just once in the group and will move level on points with the leaders, provided they can beat an England side bolstered by a number of recalls.
While Michael Carrick and Andros Townsend have been forced withdraw due to injuries, Saido Berahino could debut while Stewart Downing may make his first appearance since May 2012 after impressive form for West Ham.
Downing is revelling in a more central role at Upton Park this term and hopes to bring that level of performance to the international stage.
"I spoke before and said that I would probably find it difficult to get back in," he explained this week.
"It's obviously helped massively - the change in position. Playing out wide there is a lot of young talent here so you have got a lot of options in that position.
"I now need to carry that form into an England shirt and carry on playing well. I'd love to go to the Euros but just getting back in an England shirt is a big plus for me at the moment."
While England have been hit with injury withdrawals, Katanec has also had to deal with an apparent refused call-up of Josip Illicic.
According to the Slovenia coach, Fiorentina playmaker Illicic has opted not to answer the call but Katanec insisted his side will go to Wembley eager to cause an upset.
"We can go there relaxed and play a good game," explained the 51-year-old, who will be without striker Roman Bezjak due to a chest problem.
"In the last few weeks you will have seen that every game starts at 0-0, even a good team like Roma and others can concede six or seven goals. Anything is possible."
On Illicic, he added: "I had Josip Ilicic in the squad but the player decided to refuse the call-up. He did not respond to my calls or messages, letting me know he does not want to play for Slovenia as long as I am there."
