Pt-decorated CdSe tetrapods with different arm lengths were tested for the photocatalytic hydrogen generation reaction. Well-defined CdSe tetrapods with controlled wurtzite arm lengths were synthesized by the continuous precursor injection (CPI) approach. Pt nanocrystals with an extremely small size of ~1 nm were directly decorated on the overall surfaces of CdSe tetrapods. Ligand-exchanged Pt-decorated CdSe tetrapods with different arm lengths were employed as photocatalysts for photocatalytic hydrogen generation reaction in the presence of hole scavengers. Pt-decorated CdSe tetrapods with shorter arm length showed the highest photocatalytic efficiency, which is due to higher probability of charge separation.