Phosphorus-doped ZnO nanoneedle arrays were prepared by phosphorus diffusion from InP substrate using a pulsed laser deposition (PLD) technique. The optical properties of ZnO nanoneedle were investigated by photoluminescence (PL) spectroscopy. Low-temperature photoluminescence spectrum measurements exhibited five acceptor-related emission peaks. The excitation intensity and temperature dependent photoluminescence spectra confirmed that the emission peaks corresponded to neutral-acceptor bound exciton, free electron to acceptor, donor–acceptor pairs, and their first and second photon replicas transitions. Acceptor-binding energy was determined to be 135–167meV, which agrees well with the best-fitting result of the temperature dependent photoluminescence measurements and is reasonable in terms of theoretic prediction in ZnO.