Charlton's record of 49 goals from his 106 internationals has stood since May 1970 but Rooney, who has 48 in 105 matches, has the perfect opportunity to beat it when England play tiny San Marino in Serravalle in Group E on Saturday.
If he should fail, the England skipper, who has scored in England's last five qualifiers and has grabbed nine goals in his last 12 England games, will get a second chance when England play Switzerland at Wembley next Tuesday.
Victory against San Marino, who have only avoided defeat in one competitive international in the last 10 years, will virtually ensure England's qualification for next year's finals in France, and they will make absolutely certain of their place by beating Switzerland as well.
England top the group with a perfect haul of 18 points from their six matches, with Switzerland trailing them on 12 and Slovenia third with nine.
Even if England win on Saturday there remains the minute mathematical chance they could finish on 21 points with Switzerland and Slovenia, but in real terms, they are virtually home and dry.
And despite a host of injuries, coach Roy Hodgson will certainly hope to see England stretch their unbeaten run in World Cup and European qualifiers to 26 when they take on San Marino.
Midfielder Jonjo Shelvey, one of the men included in the squad, partly as a result of the injuries to other players but more significantly because of his good early season form for Swansea City, says he will do all he can to help Rooney get the record on Saturday.
Last week, Shelvey, whose only cap came against San Marino in 2012, was in the Swansea side that beat Rooney's Manchester United 2-1 in the Premier League, but on Wednesday their club allegiances were put to one side.
"For me he is the best English player in England," Shelvey told a news conference at England's training base at St George's Park in the Midlands.
"He is a tremendous player, and it speaks volumes of what he is about to do. If I play, I will try and set him up to get the two goals for the record and hopefully he can do it."
England have won all five competitive matches they have played against San Marino with a goal tally of 31-1 and even without the injured Ryan Bertrand, Jordan Henderson, Jack Wilshere, Phil Jones and Danny Welbeck, they are virtually certain to win again.
San Marino coach Pierangelo Manzaroli achieved something of a minor miracle in November when his team drew 0-0 with Estonia, the first time they managed to avoid a competitive defeat in a decade.
He has little chance of repeating that relative success against England who won 8-0 at Serravalle on their last visit there for a World Cup qualifier in March 2013, when Rooney scored once.
He also scored against them in England's 5-0 win at Wembley last October.
(Editing by Sudipto Ganguly)
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