Experimental data concerning the changes in the current-voltage (I-V) perfor-mances of a molecular material-based heterojunction consisting of hexadecafluorinatednickel phthalocyanine (Ni(F16Pc)) and nickel phthalocyanine (NiPc),(Au|Ni(F16Pc)|NiPc|Al) are introduced as an unprecedented principle of transduction for gassensing performances. The respective n- and p-type doped-insulator behaviors of therespective materials are supported, owing to the observed changes in surface potential(using the Kelvin probe method) after submission to electron donor (ammonia) and electronacceptor gases (ozone). On the other hand, the bilayer device exhibits strong variations inthe built-in potential of the junction and in its rectification ratio. Moreover, large increasesoccur in forward and reverse currents in presence of ammonia vapors. These make possiblea multimodal principle of detection controlled by a combined effect between theheterojunction and the NiPc|Al contact. Indeed, this metal/organic junction plays a criticalrole regarding the steady asymmetry of the I-V profiles during the device's doping evenusing high ammonia concentrations. This approach offers a more sophisticated alternative tothe classically studied, but at times rather operation-limited, resistive gas sensors.