Suppose you had
Vector2 characterPosition; //on viewport
float characterRotation; //in radians
Suppose you also had the current mouse position
MouseState mouseState = Mouse.GetState();
Vector2 mousePosition = new Vector2(mouseState.X, mouseState.Y);
Then you could calculate the vector that points from character to mouse position
Vector2 dPos = mousePosition - characterPosition;
You could then use Math.Atan2
to get the angle that this vector forms with positive x axis. That would be the needed angle for the character, so you set it for your characters rotation:
characterRotation = (float)Math.Atan2(dPos.Y, dPos.X);