Usman Khawaja, Phil Hughes, Ed Cowan, Aaron Finch and Adam Voges are all expected to be involved in the four-day fixture starting at the Sydney Cricket Ground on November 13.
Australia are due to announce their squad for the first Test in Brisbane one day before England begin their warm-up match.
Cricket Australia's executive general manager of team performance Pat Howard explained the reasons for adding the extra batsmen to the NSW team.
"We feel this match presents a good opportunity to give a core group of talented batsmen from a number of states further experience against a strong international line-up," he said.
"We continue to look for opportunities to develop our batsmen, and taking part in matches like this only helps in that area."
The switch appears to signal a reciprocal arrangement for future Australian Ashes touring teams in England.
"The ECB is supportive of this plan," added Howard.
"It wanted us to field a strong line-up, so we will use the opportunity to promote key players in the Australian system.
"In return, we look forward to the ECB fielding powerful teams for the touring Australian side in 2015.
"We appreciate the cooperation of all the state associations in supporting this plan, particularly as it coincides with the third round of (Sheffield) Shield matches."