Most often, only TOC and the concentrations of the 16 PAHs of the US EPA list are monitored in contaminated soils of former coking plants or MGPs. The objective of the present study was to provide a detailed characterization of the organic extracts of (i) coal tar particles sampled from a contaminated soil and (ii) of water at equilibrium with these particles. Chromatographic techniques were used (HPLC, GC–MS) as well as Fourier Transform Infrared Microscopy. An accurate description was obtained, showing the predominance of aromatic compounds in the coal tar and the preferential transfer of polar compounds and aliphatic hydrocarbons into water.