From a vehicle arson case, it briefly introduced the basic situation and investigation of fire, particularly discussed the inspection process of samples, even compared some main components with suspected criminal tool at length. The results showed that it was deteced gasoline composition in extracted material evidence of vehicle combustion residue,but the vehicle were diesel fuel car. Then it analysed in detail the difference of gasoline, diesel oil and mixture of gasoline and diesel oil on composition. Their composition characteristics were both have aromatic hydrocarbons, such as dimethylbenzene series, trimethylbenzene series, tetramethylbenzeneseries, methylindane, naphthalene series, But alkane composition and distribution was not the same, as diesel contained C11-C20 linear paraffin and branched paraffin which obviously normal distribution, even the content of alkanes was significantly higher than aromatic hydrocarbon.but gasoline was different , not only the alkane characteristics is not obvious, but also aromatic hydrocarbons high content; While the content of alkanes and aromatic hydrocarbon were similar in mixture. By comparing the plastic drum left on scene with inspected samples, their gasoline characteristics were the same, Thus we can determine the plastic drum was criminal tool of setting fire, it could provide powerful evidence to solve cases for fire investigators and criminal investigators.