Sugar-based ionic surfactants forming micelles are known to suppress ESI of various compounds due to decrease in surface tension upon micelle formation [1]. For the first time, poly (sodium N-undecylenyl-alpha-D-glucopyranoside 4,6-hydrogen phosphate, (poly-alpha-D-SUGP) based surfactants with different chain lengths and head groups have been successfully synthesized, characterized, and applied as compatible chiral selector for MEKC-ESI-MS/MS. First, the effect of polymerization concentration of the monomer, alpha-D-SUGP, was evaluated by enantioseparation of one anionic compound (1,1 alpha-binaphthyl-2,2 alpha-diyl-hydrogen phosphate) and one zwitterionic compound (dansylated phenylalanine) in MEKC-UV to find the optimum molar surfactant concentration for polymerization. Next, MEKC-UV and MEKC-MS were compared for the enantioseparation of 1,1'-binaphthyl-2,2 alpha-diyl-hydrogen phosphate. The influence of polymeric glucopyranoside based surfactant head groups and carbon chain lengths on chiral Rs was evaluated for two classes of cationic drugs (ephedrine alkaloids and beta-blockers). Finally, enantioselective MEKC-MS of ephedrine alkaloids and beta-blockers were profiled at their optimum pH 5.0 and 7.0, respectively, using 20 mM NH4OAc, 25 mM poly-alpha-D-SUGP at 30 kV and 25 degrees C under optimum spray chamber conditions. The LOD for most of the enantiomers ranges from 10 to 100 ng/mL with S/N of at least >= 3.0.