Multipod-like zinc oxide (M-ZnO) whiskers were produced in bulk quantity by the thermal oxidation of metal Zn powders that had been etched by an NiSO4 aqueous solution. X-ray diffraction, scanning electron microscopy and energy dispersive x-ray analysis investigations showed that the M-ZnO whiskers had pure hexagonal structure with several needle-like legs united at a common junction. A weak photoluminescence emission band peak around 380 nm and an intensive one around 495 nm were observed in the M-ZnO whiskers, which have been attributed to the near band-edge emission and the deep-level emission related to oxygen vacancy, respectively.