This study investigated the effect on reducing the pressure rise rate(PRR) in HCCI Engine by the variation of mixing ratio in the pre-mixture of DME and n-Butane that has different auto-ignition characteristics. In addition to measure of gas pressure in the engine cylinder, chemiluminescence image using the optical accessible engine and numerical analysis with multi-zones model were used to assess the combustion at each local area in the combustion chamber. The maximum PRR changes depending on mixing condition of DME and n-Butane. When DME is stratified and n-Butane is distributed uniformly, maximum PRR becomes lowest which is about 0.25MPa/ms and it corresponds to 5deg. retarding of CA50.