Hope Powell's side will use the game against London 2012 Olympic bronze medallists Canada on April 7 as preparation for Euro 2013.
It is the first time the New York Stadium, opened in August, has been chosen as a venue for an international fixture.
"We feel privileged that the Football Association have granted Rotherham the opportunity to host this international game at the New York Stadium," said Millers chairman Tony Stewart.
"When we opened the New York Stadium, we wanted to showcase it to the biggest audience we could and after a number of sell-outs we are set to capture a new audience.
"We look forward to putting our home on show for the world to see, in what I believe will be a very good game."
The match against Canada is one of two internationals which form part of FA150 celebrations, helping to mark the FA's 150th anniversary. The other is against Japan at Burton.