A new kind of crown ether, OH-dibenzo-14-crown-4 (OH-DB14C4), is prepared and coated onto the fused silica capillary by sol-gel process. Chromatographic characteristics including column efficiency (> 3,000 plates/m), thermal stability (to 330 degrees C) and ability of deactivation are studied. The selectivity of new stationary phase is superior to sol-gel OH-terminal silicone oil (OH-TSO) for positional isomers of some aromatic compounds such as xylene, dichlorobenzene, nitrotoluene, nitrochlorobenzene. The new stationary phase has high sample capacity for separation of small molecular mass compounds: low-molecular-mass alcohols, ethers and ketones, short-chain fatty acids and volatile amines.