Successful remediation of oil-contaminated soils relies on a sound preceding characterization of the oil chemical composition and physicochemical properties. Comprehensive two-dimensional gas chromatography with flame ionization detection (GCxGC/FID) is known to be very suitable for the analysis of complex samples such as petroleum hydrocarbons. However, in spite of the high-separation power offered by GCxGC, it fails to completely separate certain hydrocarbon groups in petroleum hydrocarbon mixtures. This hampers a detailed chemical composition assessment which can lead to wrong conclusions on the behaviour of the oil in soil systems, e.g. biological degradability and water solubility. This paper describes a high-performance liquid chromatography (HPLC) system with a silver-modified column as a prefractionation step to GCxGC to improve chemical identification. With HPLC, the petroleum hydrocarbons were baseline separated into a saturated fraction (including alkanes and cycloalkanes) and an unsaturated fraction (including alkenes, aromatic hydrocarbons and heterocyclic components). Each fraction eluted in a small time window limiting the dilution caused by HPLC. The two fractions were collected and quantitatively analyzed with GCxGC/FID. Cold splitless injection of 4 microl was adopted to compensate the dilution caused by the prefractionation step. With oil-spiked soil samples, a good reproducibility was obtained (RSD=3.5%; n=7) and the recovery was satisfactory (87.7%).