In this work, a new type of hydrophobic stationary phase that provide electrostatic interactions with analytes was developed by bonding β-phenylethylamine as a functional ligand to silica. This stationary phase can separate proteins with similar hydrophobicity that traditional hydrophobic resins cannot. Hen egg white was separated to examine the selectivity. The results show that the introduced electrostatic interactions are an important factor for the resolution enhancement and the new resin could have important applications in separation and purification of biological macromolecules.