Metal doping has been demonstrated to be an effective strategy to modulate photocatalytic properties. However, it is very challenging to achieve tunable electronic structures and controllable morphologies with more active sites only via metal doping. Herein, Zr doped CaTiO3 photocatalysts with enhanced photocatalytic activities toward the hydrogen evolution was prepared by one-step mild hydrothermal reaction. We revealed that zirconium doping would regulate the surface structures of CaTiO3 from smooth surface to characteristic nanosteps structures. This nanosteps structure with more exposed active sites accompanied by higher exposed surface area, oxygen vacancies and reduction ability, effectively promote the separation of photo-induced carriers, thus resulting in increased photocatalytic properties. This work provides a guideline for surface structures and electronic structures modification simultaneously to design powerful photocatalysts only by metal doping.