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This study examined the effects of fuel composition and intake pressure on two-stage high temperature heat release characteristics of a Homogeneous Charge Compression Ignition (HCCI) engine. Light emission and absorption spectroscopic measurement techniques were used to investigate the combustion behavior in detail. Chemical kinetic simulations were also conducted to analyze the reaction mechanisms in detail. Blended fuels of dimethyl ether (DME) and methane were used in the experiments. It was found that the use of such fuel blends together with a suitable intake air flow rate corresponding to the total injected heat value gave rise to two-stage heat release behavior of the hot flame, which had the effect of moderating combustion. The results of the spectroscopic measurements and the chemical kinetic simulations revealed that the main reaction of the first stage of the hot flame heat release was one that produced CO from HCHO.