Aziz Behich and Dean Bouzanis have both been picked up by Eredivisie clubs prior to the European window slamming shut.
After impressing in Turkey for previous club Bursapor and starting all three of the Socceroos games at the World Cup, Behich attracted the interest of PSV.
The reigning Eredivisie champions are now coached by former Socceroos assistant Mark van Bommel and also signed fellow Australian Trent Sainsbury in August.
Behich, who has spent the past five seasons in Turkey, revealed a call from van Bommel was too hard to turn down with Champions League football likely another big factor in his decision.
“He called me if I was interested in a switch and from that moment on my decision was made,” Behich said.
“Mark is a great coach and besides him, Trent Sainsbury convinced me. He pushed me almost daily to also come to PSV.
“You do not get the chance every day to play at a prestigious club like PSV who also play the type of football, which I love.”
While Behich has joined PSV permanently in a transfer rumoured to have been worth around $4 million, Australian goalkeeper Dean Bouzanis will instead spend the season on loan with PEC Zwolle.
The Melbourne City shot stopper will link up with former City coach and now PEC manager John van 't Schip.
Bouzanis arrives as cover for an injured Diederik Boer, but the Dutch club do have the option to buy the 27-year-old at the end of the season depending on how things go.
The former Liverpool youth player joins fellow Australian Denis Genreau at Zwolle, who is also there on loan from City.
PSV and PEC incidentally faced off in their most recent Eredivisie match with van Bommel's side claiming a narrow 2-1 win.
That result saw PSV maintain a perfect start to the season and sit top of the ladder, while Zwolle have now lost all three of their games to date and sit bottom.