In this paper, a method, based on the prediction of the Kovats retention indices of related polysubstituted alkylbenzenes from the indices of benzene, monsubstituted alkylbenzenes and disubstituted alkylbenzenes, was used to aid qualitative analysis with mass spectrometry alone. A disproportinated aromatic product and the basic compounds of alkylbenzene were analyzed with gas chromatography isothermally at 100 degrees C separately. In order to cut down the analysis time and increase the resolution, the disproportionated aromatic product was analyzed using temperature programming with gas chromatographymass spectrometry (GC-MS). The Kovats retention indices of the basic compounds were determined and those of the polysubstituted alkylbenzenes were predicted with the method which was proposed by us previously. The isomers of polysubstituted alkylbenzenes have similar mass spectra, so they can not be identified unambiguously by MS alone. For the differences of the Kovats retention index between isomers of polysubstituted alkylbenzenes are larger, it can be identified by matching the experimental retention indices with the predicted ones. The positional isomers of polysubstituted alkylbenzenes which are very difficult to be interpreted by MS alone have been identified explicitly.