We study properties of the line at 3.33 eV observed in photoluminescence (PL) emission spectra of various ZnO films prepared using pulsed laser deposition method. The influence of deposition parameters, such as oxygen pressure, laser fluence, post-annealing, and electric field exposure on intensity of this luminescence band has been investigated. The recombination characteristics are probed by temperature and excitation dependent PL spectroscopy. The obtained experimental data suggest that the 3.33 eV luminescence line in ZnO depends strongly on surface band bending and originates from recombination of bound excitons (BEs) complex located near the surface and grain boundaries. The anomalously small thermal activation energy of BE in comparison with the localization energy is explained by decreasing of the interface barrier. Possible nature of defects that bind free excitons and cause the 3.33 eV emission line in ZnO is proposed. V C 2012 American Institute of Physics. [http://dx