This work reports on a reduced graphene oxide and poly(aniline) composite (rGO-PANI), with rGO clusters inserted between PANI chains. These clusters were formed due the plasticizing effect of N-methyl-2-pyrrolidone (NMP) solvent, which was added during the synthesis. Further, this composite was processed as thin film onto an interdigitated electrode array and used as the sensitive layer for ammonia gas, presenting sensitivity of 250% at 100 ppm, a response time of 97 s, and a lowest detection limit of 5 ppm. The PANI deprotonation process, upon exposure to NH₃, rGO, also contributed by improving the sensitivity due its higher surface area and the presence of carboxylic acids. This allowed for the interaction between the hydrogen of NH₃ (nucleophilic character) and the -COOH groups (electrophilic character) from the rGO surface, thereby introducing a promising sensing composite for amine-based gases.