Homochiral (S)-[10]paracyclophane-13-carboxylic acid ((S)-1) could conveniently be obtained on a preparative scale via fractional crystallization of the (S)-1-phenylethylamide diastereomers. (S)-1 was used for the first time as a stereodifferentiating element with planar chirality for a new chiral stationary phase (CSP) for HPLC. The CSP, which was prepared by bonding (S)-1 to gamma-aminopropylsilanized silica gel via amide linkage, recognized a wide range of enantiomers by HPLC.