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It is important in the application of bio-ethanol in homogeneous-charge compression ignition (HCCI) engines to investigate the HCCI combustion characteristics of ethanol. As the inhibitory mechanism of ethanol on HCCI combustion is a key factor, simulated chemical reactions are necessary. In this study, chemical reaction simulations in the combustion chamber of a rapid compression machine (RCM) were performed in order to investigate the inhibitory mechanism of ethanol on the HCCI combustion of heptane. The sensitivity analysis results suggested that the OH radical consumption reaction by ethanol that occurs would inhibit the cool flame reaction of heptane. Furthermore, visualization of HCCI combustion with the RCM was conducted using a quartz glass combustion chamber head and ICCD camera. As a result, the cool flame luminescence intensity of heptane was reduced by the addition of ethanol.