Two amino acid-based alkenoxy micelle polymers were synthesized for this study. These include polysodium N-undecenoxy carbonyl-L-leucinate (Poly-L-SUCL) and polysodium N-undecenoxy carbonyl-L-isoleucinate (Poly-L-SUCIL). The polymerization time and concentration of the synthesized micelle polymers were optimized by H-1-nuclear magnetic resonance (NMR) and capillary electrophoresis (CE) experiments. Detailed physicochemical properties (H-1 NMR, critical micelle concentration (CIVIC), optical rotation, partial specific volume, aggregation number, and polarity) were determined, and these molecular micelles were introduced as a pseudostationary phase in micellar electrokinetic chromatography to study the molecular recognition and to develop a method for simultaneous separation of eight chiral beta-blockers. It is found that poly-L-SUCL gives overall better chiral resolution and wider chiral window than poly-L-SUCIL. After optimizing the type of micelle polymer, injection size and temperature, simultaneous separation and enantioseparation of eight beta-blockers were achieved in less than 35 min. A comparison with the amide-type surfactants of the same polar head group and alkyl chain length showed that carbamate-type surfactants always work better than the corresponding amide-type surfactant.