Milicic was announced as interim coach of the Australian women's national team by Football Federation Australia on Monday and will name his first squad in the coming days ahead of the Cup of Nations tournament later this month.
The 44-year-old, a former Australia international, was a Socceroos assistant under Ange Postecoglou and also coached the Olyroos.
However, the appointment is Milicic's first time in charge of a women's team.
Barbieri, one of the Matildas greatest players, was confident Milicic's lack of experience in women's football wouldn't work against him and called on Australia's players to show what they are capable of.
She said she was also excited to see what fresh ideas he would bring to the table.
“I think it is fantastic that Ante (Milicic) has put his hand up to coach the Matildas,” Barbieri said.
“He goes into this job unaware of how much he will fall in love with women’s football.
“It’s a really exciting time for the girls to have such an experienced coach and someone who has been a part of Australian Football for so long but not part of the women’s game.
“Hopefully he’s prepared to embrace women’s football and get the girls prepared for France.”
The appointment of Milicic comes a month after the shock sacking of former Matildas boss Alen Stajcic due to allegations of a toxic culture in the national squad.
The controversial axing of the popular coach has loomed over the team with Stajcic's appeal to the media for an inquiry into his dismissal only further igniting the flames of the saga.
While many of the Matildas star players have spoken out against Stajcic's sacking, they have pledged their commitment to Australia's World Cup cause.
Barbieri doesn't believe the drama will affect the Matildas at the World Cup and backed the players to perform under the leadership of Milicic.
"I don't really think it mattered who took the job," she said.
"I think the girls have become stronger together through this ordeal and should be energised to attack this next phase of their World Cup preparations with gusto.
"It is hard to fill the shoes of a coach who is so loved but its something which happens often in football.
"All the issues a side this should bring the girls closer together and work better as a unit."
One important step on Australia's lead up to the World Cup will be the Cup of Nations tournament on home soil which kicks off on February 28.
The Matildas will take on Argentina, Korea Republic and Trans-Tasman rivals New Zealand in a round robin format across three match-days taking place in Sydney, Melbourne and Brisbane.
Former Australia goalkeeper Barbieri, urged Milicic to use the tournament as a chance to take risks and experiment in order to unearth the perfect game plan for the World Cup.
"There are certain elements of the Matildas game which was worrying for a lot of fans," Barbieri said.
"Unfortunately there are a few problems with depth in the Matildas defence and also the team has struggled to create chances.
"Ante will need to work quickly to work out solutions to these problems but I'm confident he and the girls will be able to find the answer to these questions in good time.
"It's a very exciting time for the Matildas and it is important we give Ante and the girls plenty of support."
