The Scotland boss confirmed that the 22-year-old Huddersfield striker would lead his line after QPR forward Jamie Mackie pulled out through injury, and in the absence of Craig Mackail-Smith and Kenny Miller.
Rhodes, whose only Scotland appearance so far was as a late substitute against Cyprus in November, scored 40 goals for his club last season.
He also netted eight goals for the Scotland under-21s which has encouraged Levein ahead of the final warm-up game before the 2014 World Cup qualifiers begin next month with a double-header at Hampden against Serbia and Macedonia.
The former Hearts and Scotland defender said: "I had the idea that Jamie Mackie will play but obviously he has a calf strain so Jordan will play.
"You look at his goalscoring record, it is a tough one to beat, 40-odd goals last season.
"He has trained well and done exceptionally well in the under-21s side so, for me, it's a no brainer, he will start the match.
"I would like to give Matt Gilks some time on the field if possible.
"He has been along to a number of games and hasn't quite managed, for one reason or another, to get on the field.
"Most of it to be honest has been down to the form of Allan McGregor but I would like Gilksy to get a bit of time as well."
McGregor will be protected by a back four of Alan Hutton, Andy Webster, Christophe Berra and Danny Fox.
Gary Caldwell is set to anchor the midfield which includes Robert Snodgrass, James Morrison, Charlie Adam and Steven Naismith with Rhodes leading the line.
Australia coach Holger Osieck is likely to give debuts at some point to Hearts defender Ryan McGowan and Heracles' Jason Davidson.
However, there will be a familiarity about the Socceroos.
Veteran defender Lucas Neill, currently without a club, will captain Australia for the 50th time in his 84th appearance.
He said: "It is very humbling and I am truly privileged. I am in a list of captains who are some of the greats of Australia.
"Peter Wilson leads the way, Johnny Warren, Paul Wade, Paul Okon, Alex Tobin, John Kosmina and I can go on.
"I had posters of these guys growing up and so it is a truly great honour."