Fruit and vegetable processing wastes (FVPWs) provide a considerable environmental problem owing to their elevated organic content and propensity for contamination. Anaerobic digestion (AD) provides a sustainable approach for transforming these wastes into useful energy such as biogas, predominantly composed of methane (CH4). However, obstacles such as process inefficiencies and poor methane yields prevent the extensive implementation of this technique. This study investigates the application of iron oxide (Fe2O3) as a catalyst to augment biogas and biomethane generation during the anaerobic digestion of FVPW. Iron oxide is recognized for its role in promoting direct interspecies electron transfer (DIET) among microbial communities, hence accelerating the degradation of organic materials and augmenting methane generation. This study involved loading anaerobic digesters with FVPW and inoculum (anaerobic sludge) under mesophilic conditions (37 °C). FVPW was introduced into the reactors at several concentrations 3%, 4%, 5%, and 6% (w/v) with 0.5 g/L iron oxide to assess its catalytic influence on biogas production, methane concentration, and process stability. The objective of this chapter is to present iron oxide as an effective additive that substantially enhances anaerobic digestion performance. The results indicate that employing FVPW in anaerobic digestion, alongside iron oxide as a catalyst, can markedly improve biogas output and methane yield, presenting a feasible approach for sustainable energy generation from agro-industrial waste.