Microbial fuel cell (MFC), a new type of clean energy production equipment, can generate electricity while decomposing organic matter in wastewater. Facing the emergence of energy crisis, the reasonably designed MFC equipment can alleviate the current energy crisis, the generation of this new energy is green and sustainable. The conversion rate of energy is an important factor that affect the wide application of MFC, so improving the power production performance of MFC has attracted a lot of attention from scholars. Air-cathode MFC is an MFC configuration that uses oxygen as an electron acceptor to complete current transfer, that is the most promising type of MFC, but it is also accompanied by the problem of low activity of cathodic oxygen reduction reaction (ORR). Precious metal catalysts have never been able to meet the needs of practical applications, and cost-effective metal-organic framework (MOF) materials have been studied as ORR catalysts for many years. Therefore, MOF materials suitable for MFC air-cathode can be prepared as cathode catalysts to improve their power production performance through rational design. This work reviews the recent research progress of MOF and its derivatives as catalysts for modifying MFC air-cathode to improve their electricity production performance. The principles of MFC and the natural advantages of MOF materials as ORR electrocatalysts are introduced, and the latest applications of three types of materials, namely, simple MOF, MOF composites, and MOF derivatives, as MFC air-cathode catalysts are highlighted, leading to a variety of different research directions of MOF and its derivatives as MFC air-cathode catalysts. Finally, the challenges and future prospects of MOF and its derivatives in modifying MFC air-cathode to improve their power production performance are elucidated. The intention is to summarize the shortcomings exposed by MOF in modifying MFC air-cathode and provide new research ideas for the future application of MOF materials in MFC cathodes in order to promote the practical application of MFC.