A novel chiral stationary phase (CSP) was prepared by anchoring mono-6-azido-6-deoxyperphenylcarbamated P-CD onto omega-alkynyl functionalized silica (5 pm) via organic soluble Cu(I)-catalyzed Click chemistry. The obtained CSP was thereafter packed into fused-silica capillary (100 pm id) with an effective length of 9 cm and tested in aqueous CEC to separate a series of racemic aryl alcohols. High separation factors with good resolution were achieved using the current novel CSP. Some pharmaceutical compounds could also be well resolved on this newly derived CSP. The analytical results demonstrate that Click-chemistry-based perphenylcarbamated CSP affords high stability in high electric field and depicts excellent enantioseparation in CEC. The effects of pH value, buffer concentration, applied voltage, concentration of organic modifier and analyte structure on the enantioseparation are also discussed.