Federici, understudy to veteran keeper Mark Schwarzer, stood firm as Serbia peppered the goals in a frantic second half in front of a crowd of more than 28,000 on a chilly night at Docklands Stadium.
In a rematch of last year's World Cup group-stage clash in South Africa which Australia won 2-1, the Reading keeper dived to his right to stop a blazing shot from Radosav Petrovic in the 83rd minute and then repeated the feat in stoppage-time.
Both teams fielded second-string sides in the tune-up for the qualifying phase for the 2014 World Cup in Brazil starting in September and would rue a number of missed scoring chances.
Serbia midfielder Adem Ljajic was perhaps the most guilty, spraying a shot over the bar five minutes before the break after finding himself clear on goal inside the box.
James Troisi missed the Socceroos' best chance to break the deadlock when, having only the keeper to beat, he prodded a weak shot into Damir Kahriman's arms in the 79th minute.
Australia coach Holger Osieck, who rested first-team regulars Harry Kewell, Tim Cahill and Schwarzer, was pleased with the effort of his fringe players but was left frustrated by their lack of polish.
"I think I was not too happy, our game lacked a little bit of the fluid passing... we played the complicated ball instead of the simple ball," the German told reporters after recording his ninth win from 14 matches since taking charge after the World Cup.
"On the other hand, our team showed a great deal of effort again... basically, I got a lot more positives than negatives."
SECURITY PRESENCE
The match drew a heavy security presence around the stadium with concerns over crowd trouble following incidents involving Serbian fans at the Australian Open tennis in recent years.
The match had to be paused for a minute in the second half while staff extinguished one of a number of flares hurled near the pitch from a boisterous Serbian contingent behind one of the goals but otherwise passed without incident.
Australia, playing their second match in three days after beating New Zealand 3-0 in Adelaide in a friendly on Sunday, had a chance deflected away off Matt McKay in the fifth minute, but were soon on the back foot.
A rough challenge on midfielder Zoran Tosic gave Serbia a free-kick, with Ljajic sending his long-range effort just wide of the far post six minutes later before VfB Stuttgart midfielder Zdravko Kuzmanovic cannoned a 30-metre strike that shaved the near post in the 16th minute.
Forward Brett Holman briefly ignited the home crowd's hopes in the second half, finding space in front on the hour, but sent the shot over the bar before blasting another wide a few minutes later.
The Socceroos appeared to tire in the final stages and Serbia were denied by some desperate work from Federici who bolstered his standing as the heir apparent to Schwarzer.
