Cubic ZnIn(2)S(4) nanoparticles and hexagonal ZnIn(2)S(4) flower-like microspheres were controlled synthesized via a facile hydrothermal method by simply changing the metal precursors. The as-prepared samples were characterized by XRD, SEM, TEM and UV-vis DRS. It was found that the metal precursors influenced the final ZnIn(2)S(4) polymorphs, i.e., metal nitrates led to the formation of cubic ZnIn(2)S(4), while metal chlorides resulted in the formation of the hexagonal phase. The formation processes of the cubic ZnIn(2)S(4) nanoparticles and hexagonal ZnIn(2)S(4) flower-like microspheres were investigated and the mechanism of the phase formation was proposed. Although both cubic and hexagonal ZnIn(2)S(4) polymorphs exhibited photocatalytic activity for the degradation of methyl orange (MO) under visible light irradiation, the photocatalytic performances over cubic and hexagonal ZnIn(2)S(4) were different.