Australia had already locked in a friendly against Wales (12am AEDT, October 26) in Cardiff for the upcoming international window, and will play the two-time reigning European champions at Derby's Pride Park three days later.
The games loom as Kerr's first with the Matildas since tearing her ACL in January last year, with the Chelsea star expected to soon return to action at club level.
The Matildas captain famously scored an extraordinary solo goal from long range in the 3-1 loss to eventual runners-up England in Sydney in 2023.
The window will also allow coach Joe Montemurro to easily call on all his Europe-based players, in crucial preparation for March's Women's Asian Cup.
Kerr is yet to play under Montemurro, while Steph Catley, Caitlin Foord, Kyra Cooney-Cross and Ellie Carpenter headline the Australians based in the UK.
"Playing England in this October window is another key moment for the team as we continue to build towards the AFC Women's Asian Cup 2026," Montemurro said.
"England are one of the top teams in the world, and facing a team of their quality is a valuable opportunity for us to challenge ourselves.
"This match will provide a tough test that will help us assess where the team and players are at and identify areas for growth.
"It is important that we use these international windows to push our limits, develop deeper connections within the group, and continue setting the standards that will define our performance moving forward.
"The opportunity to play a quality side is important at this time in honing the team's skills and the style of play we are trying to develop as a team.
"It is also a great way to identify the players that are going to be crucial to our success at the AFC Women's Asian Cup and beyond."
The Matildas, ranked 15th in the world, have played world No.4 England seven times, recording two wins, one draw and four losses.
Australia will also have another window from November 24 until December 2, where they can play up to two games.
