A p-tert-butyl-calix[6]-1,4-benzocrown-4-bonded silica gel stationary phase (CR6BS) was first prepared via 3-glycidoxypropyltrimethoxysilane as coupling reagent for high performance liquid chromatography. The structure of the new stationary phase was characterized by diffuse reflectance infrared fourier transform spectroscopy (DRIFT), elemental analysis and thermal analysis. The chromatographic performance of the bonded-stationary phase was evaluated by using neutral, acidic and basic solutes as probes. Meanwhile, comparative study of the new stationary phase with a p-tert-butyl-calix[6]arene-bonded silica gel stationary phase (C6BS, the parent) and ODS was done under the same chromatographic conditions. The results show that the new stationary phase has an excellent reversed-phase property, which is similar to C6BS and ODS. However, the selectivities for some aromatic compounds are different from the parent phase (C6BS) and ODS, especially the latter. In one hand, as hybrid of calixarene and crown ether, CR6BS with the oxygen atoms of ether-bridge can provide the complexation sites for the solutes, lacking of C6BS. On the other hand, the rigid conformation of CR6BS may be responsible to the different performance partially. CR6BS exhibits high selectivity in the separation of alkylated aromatics from their parents as compared with C6BS.