A new visible-light-driven photocatalyst CsLaSrNb2NiO9 based on the 2-D layered perovskite crystal structure was prepared by using the solid-state method. Photocatalytic H-2 evolution from the aqueous CH3OH solution was achieved on the photocatalysts CsLaSrNb2NiO9 under UV or visible light irradiation. A possible electronic band structure of CsLaSrNb2NiO9 was proposed in regard to the complicated photocatalytic and photophysic properties.