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The biggest challenging issue in photocataly-sis is effcient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface. In this paper, we report that double metallic co-cat-alysts -Ti3C2 MXene and metallic octahedral (1T) phase tung-sten disulfide -(WS2) act pathways transferring photoexcited electrons in assisting the photocatalytic -H2 evolution. -TiO2 nanosheets were in situ grown on highly conductive -Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly dis-tributed on -TiO2@Ti3C2 composite. Thus, a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved, and the content of 1T phase reaches 73%. The photocatalytic -H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt% -WS2 ratio is nearly 50 times higher than that of -TiO2 nanosheets because of conductive -Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer effciency. Besides, the 1T-WS2 on the surface of -TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.