Milos Degenek, Brad Inman, Jamie Maclaren and Stefan Mauk have all received their first call up, while Craig Goodwin has also been included for the first time since the 2013 EAFF East Asian Cup.
However many of the Socceroos' Asian based players will not be involved - including Tim Cahill - as the match does not fall within a FIFA international break.
The selection process has been a challenging one for Postecoglou given the timing.
“Whilst it is an exciting fixture for us, it falls outside the FIFA window which means some boys, unfortunately, won’t be available for it. That includes all the boys playing in Asia and also Jason Geria who is playing for Melbourne Victory in the AFC Champions League, so we’ve taken all that into account.” Postecoglou said.
“We have had to cast the net far and wide again and at the same time I think we have come up with a squad that will be really competitive on the day.
“More importantly for me, it gives me a chance to see some further growth in some players playing against the best possible opposition.
“Due to this unique set of circumstances, we will name another squad next week for the upcoming matches against Greece where which will consider all eligible players.
Focusing on the 27 May match, Postecoglou was looking forward to the challenge.
“As an Australian, it is always a special event when we face England in any sport, probably more so with football.
“England is obviously a quality team and will be good challenge for us especially away from home.”
“I think it is constantly important that we test ourselves against the best and always against different types of opposition.
“Having come off the back of the first stage of qualifying against Asian opposition, it will be good to face up to something different and see how we are tracking with our progression.
“Ultimately we want to qualify for a World Cup, but we also want to know our game style and game plan will stand up against the very best,” concluded Postecoglou.