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To investigate the effects of fuel volatility on combustion and emissions in a diesel engine, a high-volatility fuel of n-heptane was blended into diesel fuel with different volumetric fractions (0%, 40%, 70%, 100%). A wide range of EGR rates from 0% to 65% were investigated, which covered both the conventional diesel combustion and low temperature combustion. Experiments under two engine load conditions, ∼5.2 bar and ∼10.5 bar gross IMEP were performed at 1500 rpm. The injection timing was fixed at 8°CA BTDC for all test cases. Results show that even if the ignition delay and combustion duration are nearly the same for all tested fuels, the premixed combustion fractions are increased for higher volatility fuels due to the improvement on mixing process during the ignition delay period. The indicated specific fuel consumption is decreased as using high-volatility fuels. The effect of fuel volatility on soot emissions depends on engine loads.