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In the HCCI Engine, inhomogeneity in fuel distribution and temperature in the pre-mixture exists microscopically, and has the possibility of affecting the ignition and combustion process. In this study, the effect of charge inhomogeneity in fuel distribution on the HCCI combustion process was investigated. Two-dimensional images of the chemiluminescence were captured by using a framing camera with an optically accessible engine in order to understand the spatial distribution of the combustion. DME was used as a test fuel. By changing a device for mixing air and fuel in the intake manifold, inhomogeneity in fuel distribution in the pre-mixture was varied. The result shows that luminescence is observed in a very short time in a large part of the combustion chamber under the homogeneous condition, while luminescence appears locally with considerable time differences under the inhomogeneous condition.