Manganese cobaltite nanorods (MnCo2O4 NRs) were prepared and tested as potential air-cathode catalyst for the single-chambered microbial fuel cells (sMFC). The power generation of sMFC increases with MnCo2O4 NRs loading to the cathode. The Polypyrrole (PPy) and Vulcan XC were used as conducting support to the MnCo2O4 NRs to form composites either by in situ or by mechanical mixing in the cathode fabrication. The cyclic voltammetry, linear sweep voltammetry and electrochemical impedance studies reveal that the in situ-MnCo2O4 NRs/PPy composite has higher catalytic activity than that of mechanically mixed-MnCo2O4NRs/PPy composite because of higher interfacial contact between MnCo2O4 NRs and PPy. The maximum volumetric power density with in situ-MnCo2O4 NRs/PPy, mechanically mixed-MnCo2O4 NRs/PPy, MnCo2O4 NRs/Vulcan XC and catalyst-free (only Vulcan XC) cathode was measured to be 6.11, 5.05, 4.22, and 1.77W/m3, respectively, in the sMFC. This suggests that PPy is not only a better conducting support than that of conventionally used Vulcan XC but also the cathode composite fabrication process is important for enhanced performance. The synergetic effect of MnCo2O4 NRs and PPy was found to play an important role for the improved energy recovery and it could be applied as an efficient and inexpensive cathode catalyst for the sMFC.