Livi secured their first Scottish Championship win of the season when they came from behind to beat Dumbarton on Saturday.
The victory saw John McGlynn claim his fourth point from two games since taking over as manager from Richie Burke and McCall knows they will be desperate to impress the former Hearts boss.
He also pointed out that Livi have players with top-flight experience, such as Simon Mensing, Martin Scott and Andrew Barrowman, who will be determined to take Motherwell's scalp.
McCall said: "I was at the Dumbarton versus Livingston game on Saturday and at half-time, Livingston had just lost a goal and didn't look as though they could turn it around.
"However, in fairness to John, he made some changes and they were terrific in the second half.
"Our boys are all in no doubt that if they're not fully focused and treat this 100 percent, it could be a banana skin. With the result they got on Saturday, and the lift they got from playing so well, their spirit will be good.
"They have good experienced players down the spine of the team; Mensing, Burton O'Brien and Barrowman up front, Scott in midfield as well as good youngsters like (Stefan) Scougall so we will be treating this game as seriously as any league game."