In this work, the solvent coordination molecular template effect of EN has been discussed in detail based on the microscopy analysis of the as synthesized ZnS nanostructures. As the EN concentration increases, the ZnS products evolve from symmetric NPs, 3D TPs to 1D NBs, accompanied with the microstructure transition from isotropic ZB to anisotropic WZ. The role of EN is significant in aspects of both the reaction rate control and the anisotropic growth activation due to the coordination effect between its amino groups and Zn atoms. Moreover, this modulation effect has been proved to be general for other short carbon-chain amine agents by the contrast experiments. The designed organic amine modulated solvothermal strategy could be utilized for controlled synthesis of other cubichexagonal combined II–VI nanostructures.