To obtain higher power efficiency of Residential Power Generation system(RPG), it is needed to operate system on optimized stoichiometric ratios of fuel and air. Stoichiometric ratios of fuel/air are closely related to efficiency of stack, reformer and power consumption of Balance Of Plant(BOP). In this paper, optimizing stoichiometric ratios of fuel/air are conducted through systematic experiments and modeling. Based on fundamental principles and experimental data, constraints are chosen. By implementing these optimum values of stoichiometric ratios, power efficiency of the system could be maximized.