Goodwillie will win his second cap at Hampden after Levein lost Kenny Miller to suspension and Craig Mackail-Smith to a back injury.
The 22-year-old Blackburn player is the only other listed forward in the squad and has played just 14 minutes of international football previously, as a substitute in a friendly win over the Faroe Islands last year.
Goodwillie recently returned to the fold after a serious sexual assault charge against him was dropped and has the added confidence of his recent £2million-plus move to Ewood Park.
And Levein, who handed Goodwillie his Dundee United debut, has confidence in the player ahead of the must-win Euro 2012 qualifier.
Levein, who has also lost Charlie Adam to injury and Scott Brown to suspension, said: "I put David Goodwillie in the squad for a reason - that's because I feel he's capable of playing international football.
"David would sit third in the pecking order and what a great opportunity for him.
"What an opportunity for a young lad to get a chance to play in a game of this magnitude.
"Technically he has the ability and also knowing him personally he won't be fazed by the size of this game.
"If I'm David Goodwillie it's an exciting time for me."
Adam has returned to Liverpool after coming off during Saturday's 2-2 draw with the Czech Republic due to a hip flexor problem, but Levein has Steven Whittaker available again after suspension and Grant Hanley back following a bout of tonsilitis.
Rangers full-back Whittaker may well be needed with both Alan Hutton and Phil Bardsley doubtful for the game.
Left-back Bardsley was substituted just before the Czechs netted their first equaliser and Hutton was suffering after his first competitive game of the season.
Levein, who will delay naming his team until Tuesday, said: "The other two who are a little bit doubtful are Phil Bardsley, who came off on Saturday with a dead leg, and Alan Hutton has a tight groin but I think he will be okay."
Levein has not called up any replacements.
"I thought about it but I put 25 players in the squad," he said. "We have lost a few but I still feel we have lots of options so I'm comfortable."