TheI‐Vcharacteristics of amorphous arsenic telluride (As2Te3) thin film on single‐crystalline silicon substrates exhibit similarity with the characteristics of a heterojunction formed between crystalline semiconductors and the carrier transport, which involves more than one conduction mechanism at the interface. The recombination, tunnelling, and space‐charge‐limited carrier transport takes place at the interface successively, depending on the magnitude of the applied voltage. The heterojunction properties dominate at lower voltages (below 1 V), while at the higher voltages, theI‐Vcharacteristic is determined by the As2Te3film. The temperature‐dependentI‐Vcharacteristics confirm the formation of a heterojunction at the silicon‐As2Te3(film) interface. The built‐in potential evaluated from theI‐Vcharacteristics (∼0.2 V) agrees well with the observed open‐circuit photovoltageVoc. Contrary to theI‐Vcharacteristics, theC‐Vcharacteristics resemble the characteristics of a conventional metal‐insulator‐semiconductor (MIS) structure. This can be qualitatively explained by assuming the heterojunction to have a low breakdown potential (∼1.0 V), and the junction barrier capacitance in the breakdown region to be higher than either the film or the depletion capacitance.