Hexagonal CuSCN and cubic Cu2S micro-scale crystallites have been selectively fabricated using CuCl2·2H2O and KSCN as the starting materials at 30 ℃ and 220 ℃, respectively. The results reveal that the reaction temperature plays a key role in obtaining pure phase of CuSCN and Cu2S crystallites. Nearly monodispersed Cu2S nanocrystals were prepared by introducing surfactant into reaction system. The possible reaction mechanism is also discussed.