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Dimethyl Ether (DME) is one of the major candidates for the next generation fuel for compression ignition (CI) engines. It has good self-ignitability and would not produce particulate, even at rich conditions. DME has proved to be able to apply to ordinary diesel engines with minimal modifications, but its combustion characteristics are not completely understood. In this study, the behavior of a DME spray and combustion process of a direct injection CI engine fueled with DME was investigated by combustion observation and in-cylinder gas sampling. To distinguish evaporated and non-evaporated zones of a spray, direct and schlieren imaging were carried out. The sampled gas from a DME spray was analyzed by gas chromatography, and the major intermediate product histories during ignition period were analyzed.