An electroluminescence (EL) phenomenon in unipolar-doped GaN/AlN/GaN double-barrier heterostructures—without any p-type contacts—was investigated from 4.2 K to 300 K. In the range of 200–300 K, the extracted peak photon energies agree with the Monemar formula. In the range of 30 to 200 K, the photon energies are consistent with A-exciton emission. At 4.2 K, the exciton type likely transforms into B-exciton. These studies confirm that the EL emission comes from a cross-bandgap (or band-to-band) electron-hole radiative recombination and is excitonic. The excitons are formed by the holes generated through interband tunneling and the electrons injected into the GaN emitter region of the GaN/AlN heterostructure devices.