For practical application on the HCCI engine, the solution of subjects, such as control of auto-ignition timing and avoidance of knocking, is indispensable. This study focused on the technique of controlling HCCI combustion appropriately, changing the mixture ratio of two kinds of fuel. Methane and DME/n-Butane were selected as fuels. The influences, which the mixing ratio of two fuels does to ignition timing, ignition temperature, rate of heat release and oxidation reaction process, were investigated by experiment with 4-stroke HCCI engine and numerical calculation with elementary reactions.