A novel polymer porous layer stationary phase containing the copolymer of glycidyl methacrylate and ethylene glycol dimethacrylate（GMA-EDMA） was fabricated, and applied as a porous layer open tubular capillary（PLOT） column.To obtain a suitable capillary for electrochromatography,various conditions including the polymerization time,the ratio of n-propanol/1,4-butanediol and GMA/EDMA in the polymerization mixture were optimized.Scanning electron microscopy demonstrated a nearly uniform polymer porous layer on the inner wall of the open tubular capillary column.In the capillary electrochromatographic mode,the PLOT column provided the reasonable separation of neutral,acidic and basic small molecules based on a reversed phase mechanism.After immobilizing the chiral selector human serum albumin（HSA）,the HSA-PLOT column performed a better chiral recognition for five pairs of enantiomers compared with the single-layer polymer coated open tubular capillary column modified with HSA.The intra-day, inter-day and column-to-column relative standard deviations for alkylbenzenes separated on the PLOT column were less than 1.7%,4.8% and 7.8%,respectively.