ZnO hexagonal prisms have been grown from poly (vinylpyrrolidone)-assisted electrochemical assembly onto p-type Si (111) substrate. These ZnO prisms arrays are highly (0002) orientated. The (0001) end facets and {1010} side facets of the hexagonal prisms are well defined. The photoluminescence (PL) spectrum of these ZnO prisms shows an intense ultraviolet near band-gap emission with a full width at half maximum of 86 meV at room temperature. The low-temperature PL spectrum is split into well-resolved free and bound exciton emission lines. The temperature dependence of the exciton emission intensities shows a nonmonotonic decaying behavior, which can be explained by the existence of interfacial states.