Activated carbon (AC) is a useful and environmentally sustainable catalyst for oxygen reduction in air-cathode microbial fuel cells (MFCs), but there is great interest in improving its performance and longevity. To enhance the performance of AC cathodes, carbon black (CB) was added into AC at CB:AC ratios of 0, 2, 5, 10, and 15 wt % to increase electrical conductivity and facilitate electron transfer. AC cathodes were then evaluated in both MFCs and electrochemical cells and compared to reactors with cathodes made with Pt. Maximum power densities of MFCs were increased by 9–16% with CB compared to the plain AC in the first week. The optimal CB:AC ratio was 10% based on both MFC polarization tests and three electrode electrochemical tests. The maximum power density of the 10% CB cathode was initially 1560 ± 40 mW/m2 and decreased by only 7% after 5 months of operation compared to a 61% decrease for the control (Pt catalyst, 570 ± 30 mW/m2 after 5 months). The catalytic activities of Pt and AC (plain or with 10% CB) were further examined in rotating disk electrode (RDE) tests that minimized mass transfer limitations. The RDE tests showed that the limiting current of the AC with 10% CB was improved by up to 21% primarily due to a decrease in charge transfer resistance (25%). These results show that blending CB in AC is a simple and effective strategy to enhance AC cathode performance in MFCs and that further improvement in performance could be obtained by reducing mass transfer limitations.