The development of new strategies to improve the separation of photogenerated carriers is crucial for enhancing photocatalytic efficiency of heterogeneous photocatalysts. Here, we have successfully constructed CdS/Bi/Ti3C2Tx nanocomposites with high electron-hole separation efficiency through coupling Bi and Ti3C2Tx on CdS nanorods. The average emission lifetime of the CdS/Bi/Ti3C2Tx nanocomposites can be up to ca. 6.74ns, which realizes efficient heterogeneous photocatalysis for oxidative hydroxylation of arylboronic acids and coupling of amines with high yields. The photocatalytic rates are ~15250 μmol·g-1·h-1 for 4-cyanophenol production and ~12125 μmol·g-1·h-1 for (E)-N-benzyl-1-phenylmethanimine production, which are twice and three-fold higher than those (~7500 and ~4000 μmol·g-1·h-1) of the CdS nanorods, respectively. The high photocatalytic efficiency can be ascribed to the strong electron-hole separation capacity by migrating electrons into Bi and Ti3C2Tx from CdS nanorods. In addition, the CdS/Bi/Ti3C2Tx nanocomposites also have satisfactory sustainable recycling and reuse properties. This work provids a new strategy for constructing heterogeneous metal/semiconductor nanophotocatalysts with strong electron-hole separation capacity for high-efficient light-driven organic transformations.