We present a new device called a double lateral heterojunction (DLH) as an ammonia sensor in humid atmosphere. It combines polyaniline derivatives in their poor conducting state with a highly conductive molecular material, lutetium bisphthalocyanine, LuPc2. Polyaniline and poly­(2,5-dimethoxyaniline) are electrodeposited on ITO interdigitated electrodes, leading to an original device that can be obtained only by electrochemistry and not by other solution processing techniques. Both polymers lead to highly conducting materials that require a neutralization step before their coverage by LuPc2. While the device based on polyaniline shows ohmic behavior, the nonlinear I–V characteristics of the poly­(2,5-dimethoxyaniline)-based DLH prove the existence of energy barriers at the interfaces, as demonstrated by impedance spectroscopy. It exhibits a particularly interesting sensitivity to ammonia, at room temperature and in a broad relative humidity range. Thanks to its higher energy barriers, the poly­(2,5-dimethoxyaniline)/LuPc2 DLH is the most sensitive device with a limit of detection of 320 ppb. This work paves the way for the use of substituted polyanilines in conductometric sensors not only in the field of air quality monitoring but also in the field of health diagnosis by measurement in human breath.