Hollow spherical corundum granules were introduced into a vitrified bond diamond grinding wheel as pore former. The influences of content and particle size of the hollow spherical corundum granules on porosity, flexural strength, and hardness of the vitrified bond diamond wheel samples were systematically investigated. The grinding performance of the designed vitrified bond diamond cup wheel on sapphire and 6H-silicon carbide (SiC) substrates was examined, and morphological properties of the ground surface were evaluated. Results showed that higher content and smaller size of hollow spherical corundum granules could lead to the increase of the porosity and the decrease of flexural strength and hardness. Sapphire and 6H-SiC substrates could be effectively ground by the vitrified bond diamond cup wheel containing 8% hollow spherical corundum granules. During the grinding, although a brittle mode dominated the material removal of two substrates, more ductile removals and lower surface roughness could be identified from 6H-SiC substrate than from sapphire.