Photoluminescence (PL) studies of the surface exciton peak in ZnO nanostructures at ∼3.367 eV are reported to elucidate the nature and origin of the emission and its relationship to nanostructure morphology. Localised voltage application in high vacuum and different gas atmospheres show a consistent PL variation (and recovery), allowing an association of the PL to a bound excitonic transition at the ZnO surface modified by an adsorbate. Studies of samples treated by plasma and of samples exposed to UV light under high vacuum conditions show no consistent effects on the surface exciton peak indicating no involvement of oxygen species. X-ray photoelectron spectroscopy data indicate involvement of adsorbed OH species. The relationship of the surface exciton peak to the nanostructure morphology is discussed in light of x-ray diffraction, scanning and transmission electron microscopy data.