With less than four months to the Socceroos' opening 2014 FIFA World Cup game in Brazil, Postecoglou has rung the changes with five A-League players among the selection for the 6 March (AEDT) game at The Den.
The locally based aces are Mark Milligan, Tom Rogic, Matt McKay, Ivan Franjic and the recalled Matthew Spiranovic.
Curtis Good (Dundee United), Chris Herd (Aston Villa), Massimo Luongo (Swindon Town) and Ben Halloran (Fortuna Dusseldorf) will all have the opportunity to make their Socceroos debut while Luke Wilkshire, Adam Sarota and Brad Jones will feature under Postecoglou for the first time.
After signing a deal with Watford on Tuesday, Neill is overlooked while fellow veteran Bresciano also misses out after his playing ban from FIFA.
"The door isn't closed," Postecoglou said when asked about skipper Neill's omission. "The one thing I won't waiver on is that players have to be playing regualar football."
The Ecuador game is the last hitout for the Socceroos before Australia must name a provisional 30-man squad for the World Cup in mid-May.
"The squad to face Ecuador represents the first steps in what I believe is the building of the next golden generation for Australian football acknowledging there is a need to balance experimentation and experience to achieve this," Postecoglou said.
"The Ecuador match gives this group of players an opportunity to stake a claim for the World Cup. They have been rewarded for playing consistent and strong football and shows that age and limited international experience are not barriers to opportunity.
"I was encouraged by what I saw on my scouting trip and what I’ve been watching in the A-League and other parts of the world and I’m confident that with courage and belief we can face the challenges ahead and not waver from our long term plan."
While the World Cup and beyond is a strong focal point for Postecoglou he stressed the importance of the Ecuador match with Ryan McGowan the only Asian-based player to be called up - with the likes of Josh Kennedy yet to commence their domestic league season.
"Ecuador is a very important game for us," Postecoglou said. "It’s the last game (before World Cup squad selection) and it’s a quality opponent. Ecuador made the World Cup and it will be a tough challenge for us.
"We started our journey against Costa Rica and we want to build on that."
The 23-man Socceroos squad to face Ecuador is:
Oliver BOZANIC - FC Luzern - SWITZERLAND - 1 (0)
Tim CAHILL - New York Red Bulls - USA - 66 (29)
Jason DAVIDSON - SC Heracles Almelo - NETHERLANDS 4 (0)
Ivan FRANJIC - Brisbane Roar FC - AUSTRALIA - 6 (0)
Curtis GOOD - Dundee United FC - SCOTLAND - uncapped
Ben HALLORAN - Fortuna Dusseldorf - GERMANY - uncapped
Chris HERD - Aston Villa FC - ENGLAND - uncapped
James HOLLAND - FK Austria Vienna - AUSTRIA - 12 (0)
Mile JEDINAK - Crystal Palace FC - ENGLAND - 42 (3)
Brad JONES - Liverpool FC - ENGLAND - 3 (0)
Mitchell LANGERAK - B.V. Borussia 09 Dortmund - GERMANY - 2 (0)
Matthew LECKIE - FSV Frankfurt 1899 - GERMANY - 5 (1)
Massimo LUONGO - Swindon Town FC - ENGLAND - uncapped
Ryan MCGOWAN - Shandong Luneng Taishan FC - CHINA PR - 8 (0)
Matthew McKAY - Brisbane Roar FC - AUSTRALIA - 45 (1)
Mark MILLIGAN - Melbourne Victory FC - AUSTRALIA - 26 (2)
Tommy OAR FC Utrecht - NETHERLANDS - 12 (1)
Tommy ROGIC - Melbourne Victory FC - AUSTRALIA - 8 (0)
Matt RYAN - Club Brugge KV - BELGIUM - 4 (0)
Adam SAROTA FC Utrecht NETHERLANDS 3 (0)
Matthew SPIRANOVIC - Western Sydney Wanderers FC - AUSTRALIA - 16 (0)
Dario VIDOSIC - FC Sion - SWITZERLAND - 19 (1)
Luke WILKSHIRE - FK Dinamo Moscow - RUSSIA - 79 (8)
