We present a comprehensive electronic structure analysis of structurally simple BN heterocycles using a combined UV-photoelectron spectroscopy (UV-PES)/computational chemistry approach. Gas-phase He 1 photoelectron spectra of 1,2-dihydro-1,2-azaborine 1, N-Me-1,2-BN-toluene 2, and N-Me-1,3-BN-toluene 3 have been recorded, assessed by density functional theory calculations, and compared with their corresponding carbonaceous analogues benzene and toluene. The first ionization energies of these BN heterocycles are in the order N-Me-,1,3-BN-toluene 3 (8.0 eV) < N-Me-1,2-BN-toluene 2 (8.45 eV) < 1,2-dihydro-1,2-azaborine 1 (8.6 eV) < toluene (8.83 eV) < benzene (9.25 eV). The computationally determined molecular dipole moments are in the order 3 (4.577 D) > 2 (2.209 D) > 1 (2.154 D) > toluene (0.349 D) > benzene (0 D) and are consistent with experimental observations. The lambda(max) in the UV-vis absorption spectra are in the order 3 (297 nm) > 2 (278 nm) > 1 (269 nm) > toluene (262 nm) > benzene (255 nm). We also establish that the measured anodic peak potentials and electrophilic aromatic substitution (EAS) reactivity of BN heterocycles 1-3 are consistent with the electronic structure description determined by the combined UV-PES/computational chemistry approach.