Using n-butanol as an alternative fuel can effectively alleviate the increasingly prominent problems of fossil resource depletion and environmental pollution. Combined injection technology can effectively improve engine combustion and emission characteristics while applying combined injection technology to n-butanol engines has not been studied yet. Therefore, this study adopted butanol port injection plus butanol direct injection mode. The engine test bench studied the combustion and emission performance under different direct injection ratios (NDIr) and excess air ratios (λ). Results show that with increasing NDIr, the engine torque (Ttq), peak in-cylinder pressure (Pmax), peak in-cylinder temperature (Tmax), and the maximum rate of heat release (dQmax), all rise first and then drop, reaching the maximum value at NDIr = 20%. The θ0-90 and COVIMEP decrease first and then increase as NDIr increases. NDIr = 20% is considered the best injection ratio to obtain the optimal combustion performance. NDIr has little affected on CO emission, and the NDIr corresponding to the lowest HC emissions are concentrated at 40% to 60%, especially at lean burn conditions. NOx emissions increase with increasing NDIr, especially at N20DI, but not by much at NDIr of 40–80%. With the increase in NDIr, the number of nucleation mode particles, accumulation mode particles, and total particle decrease first and then increase. Therefore, the n-butanol combined injection mode with the appropriate NDIr can effectively optimize SI engines’ combustion and emission performance.