The match will be played as a curtain-raiser to England's warm-up game against Italy at Salford City Stadium on Saturday, October 19, a week before the opening ceremony in Cardiff.
"It's a great opportunity to provide exposure to world-class opposition to some of our younger players, as well as established England players," said national coach Steve McNamara.
"The match also allows us to cover for many eventualities, including the possibility of giving some players the chance to play themselves into World Cup selection.
"There is a strong likelihood that some of the World Cup squad will be involved in the Knights game."
Samoa open their World Cup campaign against holders New Zealand on Sunday, October 27 at Warrington.