Semiconductor nanocomposites, which are composed of titanium dioxide (TiO2) nanorods, cadmium sulphide (CdS) nanoparticles (NPs), and Ni clusters, were synthesized. The following steps were adopted: (i) surfactant-capped TiO2 nanorods with controlled length were synthesized in an autoclave using oleic acid and amino hexanoic acid as surfactants. By using a ligand-exchange procedure, in which nitrosonium tetrafluoroborate (NOBF4) was used to replace the original surfactants, hydrophilic NOBF4-TiO2 nanorods were obtained; (ii) the resulting nanorods were deposited with CdS NPs and (iii) then deposited selectively with Ni clusters (as cocatalyst) on the nanocomposite surface. Under visible-light illumination of the nanocomposite, the generated electrons from the conduction band of CdS are transferred to TiO2 via TiO2/CdS interface, then to metallic Ni cluster. As a result, the electron hole separation was highly enhanced, leading to a Ni-TiO2/CdS nanocomposite with high photocatalytic performance for the production of hydrogen (H-2).