Abstract: A new calix8arene bonded stationary phase was prepared by modifying silica gel with 3-aminopropyltriethoxysilane followed by coupling with p-tert-butylcalix8arene ester. The chromatographic behavior of polycyclic aromatic hydrocarbons, benzoic esters, phthalates esters, and some monofunctional compounds of benzene is described. The baseline separation of positional isomers on the calix8arene-bonded phase had been achieved with methanol-water as mobile phase.A comparison with conventional reversed-phase C₁₈ columns shows a predominantly reversed-phase character and obvious priority for separation of positional isomers. The possible separation mechanism has been investigated in the paper.