Porous zwitterionic monolithic columns based on photo‐initiated copolymerization of N,N‐dimethyl‐N‐methacryloxyethyl‐N‐(3‐sulfopropyl)ammonium betaine and poly(ethylene glycol) diacrylate in a binary porogen system comprising isopropanol and decanol were prepared in 75‐μm‐id fused silica capillaries. The resulting monolith was evaluated by hydrophilic interaction chromatography. Inverse size‐exclusion chromatography was used to characterize the pore structure of the resulting monolith. A typical hydrophilic interaction chromatography mechanism was observed when the organic content in the mobile phase was higher than 60%. Good separations of amides, phenols, and benzoic acids were achieved. An efficiency of 75 000 plates/m was obtained. The effects of mobile phase pH, salt concentration, and organic modifier content on retention were investigated. For polar‐charged analytes, both hydrophilic interactions and electrostatic interactions contributed to the selectivity.