A mechanism of transverse charge transfer through hexagonal boron nitride (h-BN) in a MIS structure has been studied. Experimental data for charge transfer have been analyzed in terms of different models of charge transfer in insulators. It has been shown that charge transfer in h-BN is described by the model of phonon-assisted tunneling between neutral traps. The thermal and optical energies of phonon-coupled traps in h-BN have been determined. Based on charge transfer measurements, XPS spectra, and the ab initio electronic structure of intrinsic defects in h-BN it has been found that boron–nitrogen divacancies are most probably responsible for charge transfer in h-BN and transfer is provided by electrons.