A new type of stationary phase with specific structural properties and different undersurface structure (monomeric and polymeric) for liquid chromatographic separation has been prepared. This phase was applied for the separation of polycyclic aromatic hydrocarbons (PAHs), particularly those, recommended by the U.S. National Institute of Standards and Technology (NIST) and the U.S. Environmental Protection Agency (EPA). For comparative studies the commonly-used C-18 phase, with monomeric and polymeric structure created on the same batch of silica gel support, was applied. Physico-chemical and chromatographic properties were determined using different instrumental methods (porosimetry, elemental analysis, CP/MAS NMR, liquid chromatography), particularly under hydro-organic conditions.