Exploiting organic heterojunction effects in electrical devices are an important strategy to improve the electrical conductivity, which can be utilized into improving the conductometric gas sensors performances. In this endeavor, the present article reports fabrication of organic heterostructures in a bilayer device configuration incorporating octa-substituted nickel phthalocyanines (NiPc) and radical lutetium bis-phthalocyanine (LuPc2) and investigates their sensing properties towards NH3 vapor. NiPc having hexyl sulfanyl, hexyl sulfonyl and p-carboxyphenoxy moieties are synthesized, which electronic effects are electron donating, accepting and moderate accepting, respectively, also validated by cyclic voltammetry. The electronic effects of substituents in NiPc modulate the interfacial electrical conductivity and the type of the organic heterojunction formed. The electron acceptor and donor groups favor the formation of accumulation and accumulation/depletion heterojunctions, which are also correlated to negative and positive response towards NH3, respectively. Among the studied heterojunction devices, the one based on hexyl sulfanyl groups, revealed the highest and the most stable response in 10-90 ppm of NH3 and under variable relative humidity (rh) (10-70 %). Interestingly, the bilayer device having p-carboxyphenoxy substituted NiPc, exhibited ambipolar behavior such that its p-type semiconducting nature is changed into n-type at higher rh values, also demonstrated by change in its negative response into positive towards NH3.