In this study, CO2 conversion to acetate and CH4 was achieved in a flow-through laboratory-scale microbial electrosynthesis (MES) cell composed of a 3D conductive polylactic acid (cPLA) lattice cathode with electrodeposited metal electrocatalyst coatings. The MES cell with a bare cPLA cathode showed the poorest performance with the lowest H2 and CH4 production rates and low Coulombic efficiency. This was ascribed to a poor electrocatalytic activity of cPLA towards H2 production and high electrode resistivity. When the cPLA electrode was modified with metal coatings, the CH4, acetate and H2 production rate increased significantly, with the following trend: cPLA < Ni < NiFe < NiFeMn. The better performance of the metal-coated cPLA in terms of CH4 production was attributed to the lower electrical resistance, enhanced H2 production and enhanced electron transfer between the cathode and the biofilm. At the cell potential of 2.8 V, the best-performing NiFeMn cPLA cathode showed stable production of CH4 (50 ± 6 mL d−1), acetate (185 ± 27 mg d−1), and H2 (545 ± 175 mL d−1) at close to 100% Coulombic efficiency.