The mechanism that initiates thermal flames in compression ignition has been studied. Experimentally, a homogeneous charge compression ignition (HCCI) engine was used with DME, n-heptane, and n-decane. Arrhenius plots of the heat release rate in the HCCI experiments showed that rates of heat release with DME, n-heptane, and n-decane exhibited a certain activation energy that is identical to that of the H 2 O 2 decomposition reaction. The same feature was observed in diesel engine operation using ordinary diesel fuel with advanced ignition timing to make ignition occur after the end of fuel injection. These experimental results were reproduced in nondimensional simulations using kinetic mechanisms for DME, n-heptane, and n-decane, the last being developed by extending the n-heptane mechanism. Methanol addition, which suppresses low-temperature oxidation (LTO) and delays the ignition timing, had no effect on the activation energy obtained from the Arrhenius plot of heat release rate. Nevertheless, methanol addition lowered the heat release rates during the prethermal flame process. This is because H 2 O 2 formation during cool flame was reduced by adding methanol. The mechanism during the transition process from cool flame to thermal flame can be explained quantitatively using thermal explosion theory, in which the rate-determining reaction is H 2 O 2 decomposition, assuming that heat release in this period is caused by partial oxidation of DME and HCHO initiated with the reaction with OH produced though H 2 O 2 decomposition.