Two kinds of hollow shell structured nickel titanates (nanosphere, nanorod) were prepared by the microwave-assisted hydrothermal method using carbon material as the template. Their phase structure, morphology, and optical properties were well characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy (DRS). Comparing with the template-free NiTiO3 (NiTiO3-TF), the two kinds of hollow shell structured NiTiO3 have larger Brunauer-Emmet-Teller (BET) surface areas. Both NiTiO3 nanosphere (NiTiO3-NS) and nanorod (NiTiO3-NR) showed remarkably photocatalytic H2 evolution from the methanol aqueous solution under full-arc lamp and visible light. Additional, their photocatalytic activities were also determined by photo-degradation of methyl blue (MB), and the degradation yield reached nearly 100% within 100 min on NiTiO3-NR under visible light. Whatever in photocatalytic H2 evolution or MB degradation, their photocatalytic activities all followed the order: NiTiO3-NR > NiTiO3-NS > NiTiO3-TF. The higher photocatalytic activities of the hollow shelled NiTiO3 should be due to their larger BET surface areas and more utilization of the incident light.