Compression ignition of homogeneous charges in internal combustion (IC) engines is expected to offer high efficiency of DI diesel engines without high levels of NOx and particulate emissions. This study is intended to find ways of extending the rich limit of HCCI operation, one of the problems yet to be overcome. Exhaust emissions characteristics are also explored through analyses of the combustion products. DME fuel, either mixed with air before induction or directly injected into the combustion chamber of a rapid compression and expansion machine, is compressed to ignite under various conditions of compression ratio, equivalence ratio, and injection timing. The characteristics of the resulting combustion and exhaust emissions are discussed in terms of the rate of heat release computed from the measured pressure, and the concentrations of THC, CO, and NOx are measured by FT-IR and CLD. The experimental data to date show that operation without knock is possible with mixtures of higher equivalence ratio when DME is directly injected rather than when it is inducted in the form of a perfectly homogeneous fuel-air mixture. Although fuel injected early in the compression stroke promotes homogeneity of the DME-air mixture in the cylinder, it causes the mixture to ignite too early to secure good thermal efficiency and knock-free operation at high loads. Low temperature reactions occur at about 660K regardless of the fueling methods, fuel injection timing and equivalence ratio. The main components of hydrocarbon emissions turned out to be unburned fuel (DME), formaldehyde and methane.