A photoactivatable antimicrobial polymeric surface based on a porphycene derivate was efficiently prepared and evaluated to kill pathogenic microorganisms. The development of this self-sterilizing material consisted in the electrochemical polymerization of a peripherally tetra-substituted porphycene bearing benzyl-carbazole groups (Pc-Cbz). The latter were used as electropolymerizable centers, while the porphycene core triggered the photodynamic action. The electrodeposited photodynamic films (P-Pc-Cbz) were obtained in a reproducible and controllable manner. Electrochemistry studies combined with spectroscopic measurements demonstrated that the porphycene core remains unaffected after the electrodeposition process. Moreover, it retains its spectroscopic and photodynamic properties within the polymeric matrix. The photoactive layers were photostable and able to produce reactive oxygen species (ROS) by both photodynamic mechanisms. Also, the antimicrobial efficiency of P-Pc-Cbz was evaluated against two antibiotic-resistant strains (methicillin-resistant Staphylococcus aureus and Escherichia coli), exhibiting an antimicrobial action higher than 99.998% over these Gram-positive and Gram-negative bacteria. This work represents the first electropolymerization of a porphycene derivative and the first porphycene-based photobiocidal surface. P-Pc-Cbz shows great potential as an efficient self-sterilizing coating activated by visible light.