Innovative benzidine-free PANI-based inks for electrically conducive inkjet printed devices were developed and tested and the results compared with those obtained by traditional PANI. NMR investigations evidenced the presence of quinones and phenolic groups on the backbone of the innovative PANIs that are thought being responsible for the higher solubility in DMSO. A mechanism of reaction was proposed. The numerous characterizations (NMR, UV-Vis, FTIR, XPS and electrical investigations) allowed to compare protonation level, doping level, valence band maximum for both the type of PANI. The correlation among structural properties, printability, conductivity and solubility was discussed.