Solar-driven hydrogen production is the promising alternative for addressing the current issues from the fossil fuel depletion and environment pollution. By using the solar energy as the driven force, the photocatalysts could be activated to generate active electrons for the hydrogen production from water while the photogenerated holes could oxide water or substrates to produce oxygen or value-added chemicals. Although photocatalytic water splitting could maximize the utilization of photogenerated electrons and holes, and not bring any byproducts, the extremely low efficiency greatly limits its application. Therefore, the photocatalytic hydrogen production in presence of additives as the electron donors has been extensively developed. The overall efficiency for the hydrogen production could be further improved by coupling photocatalysis with other technologies. The synergistic promotion by photocatalysis and thermocatalysis is a promising approach for sustainable hydrogen (H2) production. Herein, we rationally design a perovskite-based catalyst with three dimensionally ordered macroporous structure (3DOM CaTiO3-Au) for photothermal catalytic H2 production from different substrates. The hierarchical 3DOM structure facilitates light harvesting and mass diffusion of the substrates while the gold nanoparticles (Au NPs) promote the charge separation. The photogenerated and hot electrons are oriented accumulated on the surface of Au NPs. The non-metallic gold species (Au(I)) show more active for H2 evolution. As a result, 3DOM CaTiO3-Au exhibits excellent activity for H2 production from glycerol and other substrates with hydroxyl group. This present work demonstrates a feasible approach to improve the sustainable H2 production by rationally designing and fabricating efficient photothermal catalysts.