Cerium oxide nanoparticles (CeO2NPs) in crystalline form have been synthesized by a coprecipitation method. CeO2nanoparticles were then embedded in polypyrrole (PPy) films during the electropolymerization of pyrrole (Py) on titanium substrate. The influence of poly(sodium 4-styrenesulfonate) (NaPSS) surfactant used during polymerization on the embedding of CeO2NPs in polypyrrole films was investigated. The new films were characterized in terms of surface analysis, wettability, electrochemical behaviour, and antibacterial effect. The surface and electrochemical characterization revealed the role of surfactant on PPy doping process cerium oxide incorporation. In the presence of surfactant, CeO2NPs are preferentially embedded in the polymeric film while, without surfactant, the ceria nanoparticles are quasiuniformly spread as agglomerates onto polymeric films. The antibacterial effect of studied PPy films was substantially improved in the presence of cerium oxide and depends by the polymerization conditions.