The former Western Sydney Wanderers and Karabukspor coach has been out of work since the Turkish club sacked him in December.
Popovic famously reached three Grand Finals with Western Sydney, and won the Asian Champions League in 2014. The 44-year-old has signed a three-year deal with the club.
Speaking on Foxsports, Popovic said Perth had untapped potential. 
"I'm very excited to have the opportunity to coach Perth Glory," Popovic said. "It's a club rich in football history and now we're at a stage where we want to create some new history.
"The potential W.A has for football, the passion of the fans, the people here love football. I'm very happy to have the chance to untap that potential.
"We can create new memories."
It's reported that Tony Pignata, former CEO of Sydney FC, will also take up the Executive role - replacing former CEO David Filopoulos - as Perth Glory instate an experienced restructure of the club under owner Tony Sage. 
Pignata was responsible for a stark turnaround in the Sky Blues on and off the pitch during his tenure, culminating in their 2017 A-League Premiership / Championship double.