A novel two-stage zinc oxide (ZnO) hexagonal microprisms was successfully synthesis via a hydrothermal route on a nickel (Ni) thin films. The Ni thin films are deposited by using magnetron sputtering onto Si (100) substrate. The formation of the secondary structure and optical properties of ZnO microprism have been investigated and the formation mechanism has been discussed. The results illustrate the Ni substrate is a key factor to grow the two-stage ZnO, and the photoluminescence (PL) emission peak at 389 nm reveals that the high crystal quality of these nanorods. ZnO with its excellent luminescent properties and the controllable nanostructures will hold promise for the development of photonic devices.