The coupling of chiral micellar electrokinetic chromatography (CMEKC) to mass spectrometry (MS) using conventional surfactant [above the critical micelle concentration (cmc)] is very challenging. Preliminary investigation in this laboratory indicates that the use of a chiral polymeric surfactant provides one possible solution to this difficult coupling. This is because of many positive attributes of micelle polymers which include zero cmc, lower surface activity, low volatility, high electrophoretic mobility, and function as a suitable separation medium even at lower concentrations of pseudophases. In this work, the feasibility of using poly(sodium N-undecanoyl-L-valinate (poly-L-SUV) in CMEKC-MS is demonstrated. After CMEKC separation, enantiomers of 1,1'-binaphthol (BOH) were detected using electrospray ionization mass spectrometry (ESI-MS) by selected ion monitoring (SIM) in the negative ion mode. Although in the SIM mode ESI-MS parameters (nebulizer pressure, drying gas flow rate, drying gas temperature, and sheath liquid flow rate) affected only the signal-to-noise ratio of (+/-)BOH, two of the ESI-MS parameters (nebulizer pressure, sheath flow rate) were found to have a significant impact on chiral resolution of (+/-)BOH. At the optimum ESI-MS conditions, the enantioseparation of (+/-)BOH was successfully accomplished by varying the buffer pH, concentration of the volatile background electrolyte, and poly-L-SUV.