The scope of this research study pertains to compare the combustion and emission behavior between naphtha and dieseline at different combustion modes. In this study, US dieseline (50% US diesel + 50% RON 91 gasoline) and EU dieseline (45% EU diesel + 55% RON 97 gasoline) with derived cetane number (DCN) of 36 are selected for experimentation in an optical engine. Besides naphtha and dieseline, PRF60 is also tested as a surrogate fuel for naphtha. For the reported fuel with same RON = 60, the effect of physical properties on combustion homogeneity when moving from homogenized charge compression ignition (HCCI) to compression ignition (CI) combustion is studied.The combustion phasing of naphtha at an intake air temperature of 95 °C is taken as the baseline data. The engine experimental results show that higher and lower intake air temperature is required for dieseline mixtures to have same combustion phasing as that of naphtha at HCCI and CI conditions due to the difference in the physical properties. Especially at HCCI mode, due to wider distillation range of dieseline, the evaporation of the fuel is affected so that the gas phase mixture becomes too lean to auto-ignite. However, at partially premixed combustion (PPC) conditions, all test fuels required almost same intake air temperature to match up with the combustion phasing of baseline naphtha. From the rate of heat release and combustion images, it was found that naphtha and PRF60 showed improved premixed combustion when compared dieseline mixtures. The stratification analysis shows that combustion is more stratified for dieseline whereas it is premixed for naphtha and PRF60. The level of stratification linked with soot emission showed that soot concentration is higher at stratified CI combustion whereas near zero soot emissions were noted at PPC mode.