Polyaniline nanofibres are typically synthesized in a two-phase system with aniline placed in one liquid phase and the initiator in the other. The authors modified this method by introducing the monomer as a salt, thus creating a third, solid phase. This salt is in the organic phase as acetonitrile. Salts of aniline+DBSA and aniline+CSA were examined. As both these salts have limited solubility in acetonitrile, they do not dissolve during polymerization. To further reduce their solubility, acid was also added to both liquid phases. DBSA and CSA were used in the organic phase while in the aqueous phase, hydrochloric acid, sulfuric acid, DBSA and CSA were used along with the initiator (APS). Numerous polymerizations were carried out to examine various phase compositions. SEM, FTIR and UV-Vis observations revealed interesting properties of the polyaniline obtained in this way. Its morphology and spectroscopic properties strongly depend on the combination of the components used in each phase. Amorphous polyaniline was obtained as were well-developed spatial forms such as blades, spheres or nanofibres.