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In this study, experimental and simulation investigations on the roles of charge density (ρtdc), temperature (Τtdc) at the top dead center and oxygen concentration (φO2) on the combustion paths, emissions and thermal efficiency of a high load operation diesel engine were conducted. Experimental engine was a modified single-cylinder engine equipped with variable mechanisms of boost, exhaust gas recirculation (EGR) and intake valve closing timing (IVCT) to regulate the Ptdc, φO2 and Τtdc. Simulations of engine combustion processes were performed with an ECFM-3Z combustion model. The results revealed that higher Ptdc, leading to lower overall fuel/oxygen equivalence ratio (Φm), enhanced the rate of mixing and chemical reaction and benefited improvement of the thermal efficiency.