This paper experimentally and numerically investigates the effects of injection timing on combustion of a methanol/dimethyl ether (DME) dual-fuel compound at various methanol concentrations. In this dual-fuel compound combustion approach, methanol is directly injected into the cylinder, and DME is injected at the intake port. The experimental results indicate that methanol injection timing has an obvious effect on the heat release process of the dual-fuel compound combustion, and the effect of methanol concentration (i.e., the engine load) on injection timing is also evident. Late injection should be adopted to achieve smooth combustion and low NOx emissions at high methanol concentrations. Moderate injection timing should be adopted to achieve higher indicated thermal efficiency (ITE) at low methanol concentrations. The simulation results, using computational fluid dynamics (CFD) combined with reduced chemical kinetics, show that methanol injected at −26 °CA after top dead center (ATDC) has a remarkable ...