Recovery of valuable metals via leaching printed circuit boards (PCBs) has gained moment recently. This work studied the Microbial fuel cell (MFC) performances for recovery of Cu from a Cu2+ solution by examining key operating parameters. A dual-chamber MFC with 6 cm × 6 cm × 7 cm dimensions was constructed. Both anode and cathode electrodes were made of a carbon cloth sheet. The anodic and cathodic chambers were separated by a Nafion membrane. The highest Cu recovery efficiency was 99.7% after 240 h batch mode operation, yielding 102 mW/m2 MFC power density output using 1 g/L Cu2+ solution as the catholyte (initial pH 3) and an anolyte containing 1 g/L sodium acetate inoculated with a sludge from a wastewater treatment plant’s anaerobic pond, with 2 cm distance between the electrodes made of polyacrylonitrile polymer. The highest open circuit voltage, current density (based on cross-section cathode area) and power density with an external load of 1 kΩ was 555 mV, 347 mA/m2 and 193 mW/m2, respectively. Additionally, recovery of Cu in the leachate of PCBs using sulfuric acid leaching after 48 h was performed and the highest Cu recovery was 50% in 48 h.