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The chemical composition of marketed gasoline varies depending on the crude oil, refinery processes of oil refineries, and season. The combustion characteristics of HCCI engines are very sensitive to the fuel composition, and a fuel standard for HCCI is needed for HCCI vehicles to be commercially viable. In this paper, the effects of the structure of the fuel components on auto-ignition characteristics and HCCI engine performance were investigated. The engine employed in the experiments is a research, single cylinder HCCI engine with a compression ratio of 14.7. The intake manifold was equipped with a heater attachment allowing control of the intake air temperature up to 150 °C at 2000 rpm. Thirteen kinds of hydrocarbons, 4 kinds of paraffins, 3kinds of naphthenes, and 6 kinds of aromatics, were chosen for the investigation, and 20vol% of each of the pure hydrocarbons was blended with the 80 vol% of PFR50 fuel.