This study investigated the effect of KOH activation on biochar, with a focus on how porosity and potassium content influence microwave-assisted catalytic biodiesel production, using experimental design approaches. Activated biochar was synthesized from oat hull waste through KOH activation, followed by pyrolysis under controlled conditions. The biochar was characterized through chemical, morphological, and physical analyses, and its catalytic performance in converting used waste cooking oil (WCO) into biodiesel was evaluated using methanol as the acyl acceptor and microwave irradiation to optimize the reaction via experimental design. Results revealed that increasing the KOH/biomass ratio significantly enhanced the specific surface area (SSA) of the catalyst, achieving a maximum SSA of 637.28 m²/g under optimal pyrolysis conditions: 600 °C for 3 h with a KOH/biomass ratio of 2. A maximum fatty acid methyl ester (FAME) yield of 100% was achieved within 1 min of microwave-assisted reaction using an optimized catalyst dosage of 2.5%, a WCO/MeOH molar ratio of 1/12, and a reaction temperature of 150 °C, with the catalyst being successfully recycled across three cycles. An economic and energy evaluation estimated a catalyst production cost of USD 176.97/kg and a biodiesel production cost of USD 8.9/kg of FAMEs. This research provides a straightforward and cost-effective approach for biofuel production.