Rectifyingp‐njunctions have been formed betweenn‐type Ge20Bi11Se69bulk glass andp‐type chalcogenide films such as Ge20Se80and As2Se3. The forward current in the power law increased with increasing bias voltage, suggesting that it was space charge limited. The spectral response of the short circuit currents showed a maximum and a shoulder at photon energies which corresponded to the optical band gaps of thep‐type films and then‐type glass, respectively. This finding is indicative of the bending of the energy bands in both thep‐type films and then‐type glass in the vicinity of thep‐type film/n‐type glass interface.