Novel optically active carbonate-type cationics were designed and synthesized via a green method. A series of n-alkyl N,N-dimethylaminoalkyl carbonates was prepared via a two-step successive carbonate exchange reaction of diphenyl carbonate with 1-alkanol followed by the reaction of the optically active or racemic amino alcohol in the presence of triethylamine. The quaternarization of the N,N-dimethylamino group was carried out using methyl iodide. Furthermore, optically active cationics were prepared by the lipase-catalyzed enantioselective hydrolysis of the racemic cationics. Carbonate-type cationics having an isopropylene linkage showed high hydrolytic stability. They exhibited surfactant properties similar to those of the corresponding racemic cationics. Although no significant differences in the antimicrobial activities were observed owing to the stereochemistry of the cationics, the biodegradability was strongly influenced by the stereochemistry. Some optically active cationics were rapidly biodegraded by activated sludge.