The chemical kinetics model studies have been conducted in this paper to assess ignition characteristics of coal-based naphtha (with carbon range C₃–C₁₀, RON of 54) for use in advanced engines. Reactivity of coal-based naphtha (CBN) was compared with two surrogate models: PRF54 (46 mole% n-heptane/54 mole% iso-octane) model and 3-component (42.561 mole% NC₇H₁₆, 43.683 mole% IC₈H₁₈ and 13.756 mole% IC₆H₁₄) model. Both two models reasonably predicted the ignition delay times (IDTs) of CBN at 10, 15 bar and 640–900 K. In addition, the experimental and simulation study of coal-based naphtha HCCI combustion was carried out. CHEMKIN-PRO software was used to simulate the effects of intake temperature (T_in) and equivalent ratio (Φ) on the combustion process of naphtha HCCI engine. The results show that the combustion of coal-based naphtha HCCI is sensitive to the T_in. With the increase of T_in, the combustion phase of HCCI is obviously advanced, the concentration of OH and HO₂ increases in the middle and low temperature reaction process, and the corresponding curve moves forward as a whole. The change of Φ has little effect on the concentration of OH and HO₂ before ignition, and the change of ignition time with the mixture concentration is not obvious. It should be pointed out that when the T_in is high or mixture is rich, the coal-based naphtha HCCI engine is prone to knock, and the peak phase will appear before top dead center (TDC). This phenomenon is especially obvious when the T_in is very high. It can be seen that the coal-based naphtha is suitable for low-temperature lean combustion.