The retention behaviour of racemic 1-(4-aminophenyl)-1,2,3,5-tetrahydro-7,8-methylendioxy-4H-2,3-benzodiazepin-4-one derivatives with anticonvulsant activity on several chiral stationary phases was investigated. The selective performances of six polysaccharide phases, namely, Chiralcel OA, OD, OF, OG, OJ and Chiralpak AD were studied and normal phase HPLC methods were optimized to separate the enantiomeric forms of this class of compounds. The chiral recognition mechanism between the analytes and the chiral selectors was discussed. A molecular modeling study was carried out with the aim to explore the enantioselective molecular recognition process with the Chiralcel OG stationary phase.