The former Socceroos striker will return to his native Sydney as coach Tony Popovic's No.2, while several other backroom posts have also been filled at the Wanderers
Announced by Wanderers executive chairman Lyall Gorman, Milicic will serve as inaugural coach Tony Popovic's No.2, while Ron Corry has been appointed goalkeeper coach and Trevor Morgan will guide the club's National Youth League side.
Rounding out the new arrivals is the appointment of former Newcastle Jets chief executive officer John Tsatsimas as general manager football operations.
"To have this calibre of coaches joining us at Wanderers FC provides a great foundation for the playing group," Gorman told the A-League website on Wednesday.
"Not only are these appointments some of the best football coaches this country has to offer, they all truly understand the DNA and culture of Western Sydney.
"With our playing squad starting to take shape, I am excited about our first training session together.
"These are the first of many more exciting football related announcements that will be occurring over the next month."
Former Australia striker Milicic returns back to his native Sydney after a two-year stint as an assistant coach under John Van 't Schip at the Heart, who overlooked him in favour of John Aloisi when it came time to choose a replacement for the Dutchman.
Corry won 27 caps for the Socceroos from 1967 to 1973 - despite being just 172cm tall - and has had head coach roles at Sydney United and the Wollongong Wolves.