Programmable photocatalysts for hydrogen evolution have been fabricated based on multi-segmented CdS-Au nanorod arrays, which exhibited high-efficiency and programmability in hydrogen evolution as the photoanodes in the photoelectrochemical cell. Multiple different components each possess unique physical and chemical properties that provide these cascade nanostructures with multiformity, programmability, and adaptability. These advantages allow these nanostructures as promising candidates for high efficient harvesting and conversion of solar energy.