Anaerobic digestion (AD), as an eco-friendly biological process, shows potential for the decomposition of leachate produced by waste incineration power plants. In this study, the effects of Fe oxides nano-modified pumice (FNP) were investigated on the fresh leachate AD process. Firstly, a simple hydrothermal method was used to prepare FNP, then introduced into the UASB reactor to evaluate its AD efficiency. Results showed that the inclusion of FNP could shorten the lag phase by 10 days compared to the control group. Furthermore, cumulative methane production in the FNP group was enhanced by 20.11%. Mechanistic studies suggested that hydrogenotrophic methanogenesis in the FNP group was more pronounced due to the influence of key enzymes (i.e., dehydrogenase and coenzyme F420). Microbial community analysis demonstrated that FNP could enhance the abundance of Methanosarcina, Proteobacteria, Sytrophomonas, and Limnobacter, which might elevate enzyme activity involved in methane production. These findings suggest that FNP might mediate interspecies electron transfer among these microorganisms, which is essential for efficient leachate treatment.