Biphenyl columns are currently available from several HPLC column manufacturers. Their biphenyl phases are only mono-functional. The tri-functional biphenyl stationary phase was modified on a coreshell silica and end-capped double at the high reaction temperature. Tri-functional biphenyl stationary phase was compared with the mono-functional biphenyl stationary phase not only for measurement of hydrogen bond capacity, hydrophobicity and steric selectivity but also for a peak shape of a metal chelating compound and basic compound. Furthermore, the stability of each biphenyl stationary phase was evaluated under both acidic and basic pH conditions. Although the phenyl stationary phase shows higher hydrogen bond capacity than the alkyl stationary phase, the biphenyl stationary phase showed the highest hydrogen bond capacity. Such a high hydrogen bond capacity led to unique separation selectivity when separating o; m; p; methyl hippuric acid and nucleic bases. The proposed tri-functional biphenyl stationary phase showed the most stability under both acidic and basic pH conditions.