A novel polymer-based particles was introduced as a stationary phase in liquid chromatography (LC). Spherical particles of a copolymer, poly(benzoguanamine-co-formaldehyde) (BF), was packed into a conventional blank LC column and the retention behavior of polycyclic aromatic compounds (PACs) was evaluated in reversed-phase LC. The trend for the retention was compared with that obtained on commercially-available octadecylsilica (ODS) and phenylbutylsilica (PBS) phases. In terms of the trend on the retentivity for PACs, the BF phase showed a similar behavior as that on the ODS phase, although the selectivity to some critical pairs was somewhat different from that on the ODS phase. The results suggest that the BF phase has a retentivity basically on the basis of hydrophobic interaction between the stationary phase ligands and the solute molecule, however, at the same time, the BF phase has a different selectivity from the PBS phase for the recognition of PACs molecules. On the basis of the comparison with the PBS phase, the unique selectivity of the BF phase can be attributed to the restricted moving of the phenyl ligands.