Single crystalline ZnSe nanowires with both zincblende and wurtzite structures have been synthesized via a chemical vapour deposition method under different growth conditions. The nanowires are usually 50-80nm in diameter, and several tens of microns in length. Room-temperature photoluminescence spectra from zincblende and wurtzite ZnSe nanowires show a broad luminescence band peaked at around 2.71 eV and a deep level emission band peaked at around 2.00eV, respectively. Effects of post-growth annealing on the photoluminescence of these nanowires have been investigated. Strong room-temperature band-edge emission could be obtained from the annealed zincblende ZnSe nanowires.