Polypyrrole (PPy) films have been successfully electrodeposited on stainless steel substrates in aqueous solution. In this work, three systems of electrolytes were studied: oxalic acid, dodecylbenzenesulfonic acid (DBSA) and a mixture of oxalic acid and DBSA. A combination of XPS and TOF–SIMS revealed the formation of an iron oxalate layer at the interface between the oxalic acid-doped PPy (PPy(Ox)) and stainless steel and a thin layer of DBSA was observed at the interface between DBSA-doped PPy (PPy(DBSA)) and stainless steel. Similar to the PPy(Ox) system, an iron oxalate was also present at the co-doped PPy/stainless steel interface. Cyclic voltammetry indicated that an iron oxalate layer initially formed at the surface of the stainless steel when the co-doping system was used. The adhesion strength and corrosion performance of the PPy coating on stainless steel were evaluated by lap shear tests and an anodic potentiodynamic polarization technique, respectively. The co-doped PPy-coated stainless steel exhibited the best adhesion and a significant shift of corrosion potential to the positive direction. This finding opens the possibility for the co-doped PPy coating to be deployed as a strongly adherent corrosion inhibitor by using a simple one-step electropolymerization process.