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A HCCI engine has been run at different operating boundaries conditions with fuels of different RON and MON and different chemistries. The fuels include gasoline, PRF and the mixture of PRF and ethanol. Six operating boundaries conditions are considered, including different intake temperature (Tin), intake pressure (Pin) and engine speed. The experimental results show that, fuel chemistries have different effect on the combustion process at different operating conditions. It is found that CA50 (crank angle at 50% completion of heat release) shows no correlation with either RON or MON at some operating boundaries conditions, but correlates well with the Octane Index (OI) at all conditions. The higher the OI, the more the resistance to auto-ignition and the later is the heat release in the HCCI engine. The operating range is also correlation with the OI. The higher the OI, the higher IMEP can reach.