A quantitative model for predicting the retention times of various single- and multi-ring aromatic hydrocarbons (AH) and heteroatom-containing molecules in high-performance liquid chromatography (HPLC) is presented. The retention time behavior of 44 aromatic molecules containing one-, two-, and three-ring structures on a [3-(2,4-dinitroanilino)]propyl-silica column was investigated under subambient separation conditions. Substituent effects (their number, type, and position on the ring) on the retention behavior of these aromatic ring structures were also investigated. A quantitative structure-property relationship (QSPR) model elucidating the retention behavior of AH molecules was developed based on the obtained experimental data. It was found that the electronic properties of the molecule and its molecular geometry play a pivotal role in determining its retention in the HPLC column. The important electronic and geometric descriptors were identified using partial least squares analysis. The electronic properties of the molecule were quantified by its ionization potential and electron affinity computed from the optimized solute geometry using the PM3 energy function. The molecular Geometry was characterized by the number of rings, molecular weight, and the valence connectivity indices. The mathematical form of the QSPR model was derived using genetic algorithms, and a log-linear form of the model was found to best correlate the HPLC retention time data with the solute molecular descriptors. The QSPR model was also used to predict the retention behavior of many other AH molecules that are commonly present in most heavy petroleum streams. The results obtained in this study enhance our understanding of the AH retention behavior and are of significance in predicting the identity of chromatographic peaks and quantify the extent of overlap based solely on parameters derived from solute structure.