A novel method for the chemical fingerprinting of petroleum sulfonates has been developed. In the present study, crude oil existing in petroleum sulfonate samples is first obtained and then is analyzed by gas chromatography. Characteristic chromatographic profiles of different brands or sources of samples are established. Pattern recognition of the chromatograms is performed using multivariate data analysis. As a result, the total 15 tested samples and 8 validated samples can be well evaluated by the standards established in the article, which are in accordance to the results of interfacial tension of each sample. The method has successfully been applied to discriminate between different petroleum sulfonates, and it seems to be very promising for a variety of other applications.