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Herein we demonstrated that the shape and phase of colloidal ZnSe nanocrystals can be spontaneously tuned through tailoring the selenium precursor reactivity in a phosphine-free reaction system. Selenium species with diverse reaction activities, i. e. Se-2(2)-or Se2-, were produced by the addition of different volumes of reductant superhydride (lithium triethylborohydride). Theoretical calculation of.Gr indicates that superhydride-reduced Se-2(2-) is less active than Se2- for the reaction with a Zn precursor. Nanoparticle growth using Se(2)(2-)produces wurtzite ZnSe nanorods whereas the reaction of more reactive Se2- with the zinc precursor leads to the formation of spherical zinc blende ZnSe nanodots. This work not only provides a facile synthetic approach for the preparation of high quality ZnSe nanocrystals but also gives insights into the shape and phase control of other colloidal nanocrystals.