ZnO nanorod and nanoprism arrays have been directly synthesized on a large-area zinc substrate via a convenient solution method. The products were characterized with XRD, SEM, HRTEM, and photoluminescence (PL) spectroscopy. The influence of the solvent and the concentration of NaOH on the size and shapes of the as-prepared ZnO samples have been studied. It was found that ZnO nanorod or nanowire arrays were fabricated in alcohol, whereas ZnO nanoprisms with pyramid tips were produced in an alcohol-water mixture. The diameters of the nanorods or nanoprisms became thicker when a higher concentration of NaOH was used. Room-temperature PL spectra of the ZnO products showed a UV emission and a broad green band. The mechanism of the nanorods and nanoprisms in two systems is briefly discussed.