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Substantial effort has been devoted to utilizing homogeneous charge compression ignition (HCCI) to improve thermal efficiency and reduce emission pollutants in internal combustion engines. However, the uncertainty of ignition timing and limited operational range restrict further adoption for the industry. Using the spark-assisted compression ignition (SACI) technique has the advantage of using a spark event to control the combustion process. This study employs a rapid compression machine to characterize the ignition and combustion process of Dimethyl ether (DME) under engine-like background temperature and pressures and combustion regimes, including HCCI, SACI, and knocking onsite. The spark ignition timing was swept to ignite the mixture under various thermodynamic conditions. This investigation demonstrates the presence of four distinct combustion regimes, including detonation, strong end-gas autoignition, mild end-gas autoignition, and HCCI.