Deep ultraviolet photoluminescence (PL) emission spectroscopy has been employed to investigate the origin of the widely observed deep level impurity related donor-acceptor pair (DAP) transition with an emission peak near 4.1 eV in hexagonal boron nitride (h-BN). A set of h-BN epilayers were grown by metal-organic chemical vapor deposition (MOCVD) under different ammonia (NH3) flow rates to explore the role of nitrogen vacancies (VN) in the deep-level transitions. The emission intensity of the DAP transition near 4.1 eV was found to decrease exponentially with an increase of the NH3 flow rate employed during the MOCVD growth, implying that impurities involved are VN. The temperature-dependent PL spectra were measured from 10 K up to 800 K, which provided activation energies of ∼0.1 eV for the shallow impurity. Based on the measured energy level of the shallow impurity (∼0.1 eV) and previously estimated bandgap value of about 6.5 eV for h-BN, we deduce a value of ∼2.3 eV for the deep impurity involved in this DAP transition. The measured energy levels together with calculation results and formation energies of the impurities and defects in h-BN suggest that VN and carbon impurities occupying the nitrogen sites, respectively, are the most probable shallow donor and deep acceptor impurities involved in this DAP transition.