Scientific and technological innovation is increasingly playing a role for promoting the transition towards a circular economy and sustainable development. Thanks to its dual function of harvesting energy from waste and cleaning up waste from organic pollutants, microbial fuel cells (MFCs) provide a revolutionary answer to the global environmental challenges. Yet, one key factor that limits the implementation of larger scale MFCs is the high cost and low durability of current electrode materials, owing to the use of platinum at the cathode side. To address this issue, the scientific community has devoted its research efforts for identifying innovative and low cost materials and components to assemble lab-scale MFC prototypes, fed with wastewaters of different nature. This review work summarizes the state-of the-art of developing platinum group metal-free (PGM-free) catalysts for applications at the cathode side of MFCs. We address how different catalyst families boost oxygen reduction reaction (ORR) in neutral pH, as result of an interplay between surface chemistry and morphology on the efficiency of ORR active sites. We particularly review the properties, performance, and applicability of metal-free carbon-based materials, molecular catalysts based on metal macrocycles supported on carbon nanostructures, M-N-C catalysts activated via pyrolysis, metal oxide-based catalysts, and enzyme catalysts. We finally discuss recent progress on MFC cathode design, providing a guidance for improving cathode activity and stability under MFC operating conditions.