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The thermochemical treatment of tungsten trioxide (WO3) nanostructured films in hydrogen sulfide to obtain tungsten disulfide (WS2) layers in the WS2/WO3 hybrid structure is studied. The temperature and treatment time influence the structural-phase state, morphology, optical properties of a WS2/WO3/FTO photocathode (on fluorinated tin oxide (FTO) substrates), and its photoelectrocatalytic activity in the hydrogen evolution reaction in acidic solution is established. The sulfidation of WO3 nanoneedle films leads to the formation of a WS2/WO3 nanocrystalline hybrid structure under optimal conditions, which provides the separation of photogenerated carriers (electrons and holes) at the interphase boundaries (heterojunctions) necessary for the efficient photoactivated hydrogen evolution reaction according to Z scheme. The calculations of thermodynamic properties of the WS2/WO3 hybrid nanocatalyst show that synergistic effect of nanophases is possible in it to increase the catalytic activity of hydrogen evolution both on the basal planes of WS2 nanoclusters and on the surface of metal oxide nanoclusters. [ABSTRACT FROM AUTHOR]