Efficient charge separation is critical for the enhancement of photocatalytic activity for hydrogen generation. The porous Cd 1-x Zn x S nanosheets with twinned phase junctions were synthesized by the cation-exchange approach of inorganicorganic hybrid ZnS-diethylenetriamine nanoflakes with cadmium ions. With the synergy of the phase junctions induced by nano twins and porous structure, the hydrogen evolution average rate over the optimal sample Cd 0.5 Zn 0.5 S photocatalyst reaches 14.44 mmol h −1 g −1 without noble metal loading under visible light irradiation, corresponding to apparent quantum efficiency of 37.3% at 420 nm and solar-to-hydrogen energy conversion efficiency of 3.46%. On the one hand, twin-induced phase junctions can improve the separation efficiency of photoelectron-hole pairs, on the other hand, the large specific surface area ascribed to the porous nanosheet can effectively improve the light absorption capacity of photocatalysis, and provide more surface active sites. This study could provide a facile approach to design and fabricate advanced materials with porous twinned phase junctions for photocatalytic applications and optoelectronic devices.