Hexagonal BN (h-BN) films codoped with Mg and O atoms were grown on n-type Si and quartz substrates heated at 500°C by the sputtering of h-BN targets containing MgO. It is confirmed from Fourier transform infrared spectroscopic measurements that h-BN films are formed by sputtering h-BN targets containing 0.25mol% MgO in an atmosphere of Ar+1% O 2 . Absorption is seen at wavelengths <400nm in transmission spectrum of the film prepared from the h-BN target in an Ar atmosphere, whereas absorption is seen at wavelengths <220nm for the film prepared from the h-BN target containing 0.25mol% MgO in an atmosphere of Ar+1% O 2 . The calculated energy levels of defects and impurities of O and Mg indicate that the absorption near 400nm is originated from nitrogen vacancies, and that the absorption near 220nm is ascribed to O N –Mg B –O N complexes, where O N and Mg B denote O atoms at N sites and Mg atoms at B sites, respectively. The film prepared from the h-BN target (0.5mol% MgO) in an Ar atmosphere exhibits a low turn-on electric field of 2.2V/μm and a gentle slope in the Fowler–Nordheim plots. The gentle slope in the Fowler–Nordheim plots is not ascribed to an increase of a field-enhancement factor, but to a decrease of the work function.