Characterization of coal tar, petroleum and PVC pitches by a liquid chromatography using cellulose 3, 5-dinitrobenzoate (DNB-cellulose) as the packing material was investigated. Separation mechanism based on charge-transfer interaction between the dinitrobenzoyl group and polyaromatic compounds was expected to be useful for separation of the constituents of the pitches. First, 26 model polyaromatic compounds were tested to examine the characteristic feature of the packing material by the liquid chromatography. As the results, the compounds were found to be classified roughly into four groups with different retention volume, principally according to the number of ring condensed. The nonplanar structure and aliphatic side chain of the polyaromatic compounds also affected on the separation behavior. Both benzene soluble-hexane soluble and benzene soluble-hexane insoluble fractions of the three pitches were separated on DNB-cellulose. It was found that, coal tar pitch contains relatively large amounts of some highly condensed polyaromatic compounds with condensed rings of 4 to 5 and petroleum pitch does small amounts of such specific highly condensed polyaromatic compounds, while PVC pitch does large amounts of less condensed polyaromatic compounds and there is not significant amount of highly condensed compound in it. Thus DNB-cellulose was useful as the convenient packing material for liquid chromatography to characterize pitches.