Graphene on SiC (000) tends to grow in multiple layers and does not have a single orientation relation with the SiC substrate. It has been considered impossible to control the rotation angle of multilayer graphene on SiC (000). In this study, we grew graphene on off-axis SiC substrates with various off angles from 0° to 8° and investigated their in-plane rotation and electronic structures systematically. As the off angle toward the [110]SiC direction increased, graphene rotated by 30° with respect to SiC became less dominant and instead, graphene rotated by 30 ± 2.5° appeared. We also found that the uniformity of the graphene rotation angle was relatively high on SiC substrates with a small off angle toward the [100]SiC direction. Our results suggest that the step-terrace structure defined by the substrate off-direction and angle plays an important role in the controllability of the rotation angle of graphene.