Surrogates for JP-8 have been developed in the high temperature gas phase environment of gas turbines. In diesel engines, the fuel is introduced in the liquid phase where volatility plays a major role in the formation of the combustible mixture and autoignition reactions that occur at relatively lower temperatures. In this paper, the role of volatility on the combustion of JP-8 and five different surrogate fuels was investigated in the constant volume combustion chamber of the Ignition Quality Tester (IQT). IQT is used to determine the derived cetane number (DCN) of diesel engine fuels according to ASTM D6890. The surrogate fuels were formulated such that their DCNs matched that of JP-8, but with different volatilities. Tests were conducted to investigate the effect of volatility on the autoignition and combustion characteristics of the surrogates using a detailed analysis of the rate of heat release immediately after the start of injection. In addition, the effect of volatility on the spray dynamics was investigated by Schlieren imaging in an optically accessible rapid compression machine (RCM). The images supported the conclusions made in the IQT tests. Furthermore, apparent activation energies of JP-8 and surrogate fuels were determined based on the chemical delay periods, which could be considered as a new parameter for developing surrogate fuel.