The development of high-performance anode materials is one of the greatest challenges for the practical implementation of Microbial Fuel Cell (MFC) technology. Copper (Cu) has a much higher electrical conductivity than carbon-based materials usually used as anodes in MFCs. However, it is an unsuitable anode material, in raw state, for MFC application due to its corrosion and its toxicity to microorganisms. In this paper, we report the development of a Cu anode material coated with a corrosion-resistant composite made of Polydimethylsiloxane (PDMS) doped with carbon nanofiber (CNF). The surface modification method was optimized for improving the interfacial electron transfer of Cu anodes for use in MFCs. Characterization of CNF-PDMS composites doped at different weight ratios demonstrated that the best electrical conductivity and electrochemical properties are obtained at 8% weight ratio of CNF/PDMS mixture. Electrochemical characterization showed that the corrosion rate of Cu electrode in acidified solution decreased from (17 ± 6) × 103 μm y−1 to 93 ± 23 μm y−1 after CNF-PDMS coating. The performance of Cu anodes coated with different layer thicknesses of CNF-PDMS (250 µm, 500 µm, and 1000 µm), was evaluated in MFC. The highest power density of 70 ± 8 mW m−2 obtained with 500 µm CNF-PDMS was about 8-times higher and more stable than that obtained through galvanic corrosion of unmodified Cu. Consequently, the followed process improves the performance of Cu anode for MFC applications.