Aimed at the problem of classification of non-hydrocarbons of crude oil, the theoretical standpoint that the polarity of a compound depends on the whole structure and composition of molecule instead of a kind of heteroatom or its functional group was presented. A method was established for the systematically structural identification of nitric compounds in crude oil. The pre-fractionation of a crude oil sample into 7 fractions was performed by djadsorption column chromatography with neutral aluminum oxide and silica gel. Subsequently, the individual components were obtained by using capillary column gas chromatography, and the types of compounds were detected by a mass spectrometer. In combination with a chemometric resolution, the compounds of fraction were further identified. This method can relieve the difficulty of classical analysis in identifying those species with very low contents or without being completely separated. The structures of 168 nitric compounds in a crude oil sample were determined by this method.