Microbial fuel cells (MFCs) are promising clean energy sources for simultaneous recycling of organic waste while harvesting electricity. The electrocatalysis of the anode is crucial for improvement of the energy conversion efficiency, power density and energy density of MFCs, which is significantly related to the microbes, electrode and electron transfer scheme between the microbes and electrode. This paper reviews and discusses electrocatalysis in MFCs, particularly addressing the recent advances in anodic electrocatalysis with direct electrochemistry of genetically modified bacteria and novel electrode materials for performance improvement, and some remaining challenges to be overcome.