The effect of the di-tertiary butyl peroxide (DTBP) additive on the heat release rate and emissions of a homogeneous charge compression ignition (HCCI) engine fueled with high Research Octane Number (RON) fuels were investigated. The experiments were performed using 0%, 1%, 2%, 3%, and 4% (by volume) DTBP-RON90 blends. The RON90 Fuel was obtained by blending 90% iso-octane with 10% n-heptane. The experimental results show that the operation range was remarkably expanded to lower temperature and lower engine load with the DTBP additive in RON90 fuel. The first ignition phase of HCCI combustion was observed at 850 K and ended at 950 K while the hot ignition occurred at 1125 K for all fuels at different engine working conditions. The chemical reaction scale time decreases with the DTBP addition. As a result, the ignition timing advances, the combustion duration shortens, and heat release rates were increased at overall engine loads. Meanwhile, the unburned hydrocarbon (UHC) and CO emissions decrease sharply with the DTBP addition while the NOx emissions maintain at a lower level.