A novel poly( 4-vinylphenylboronic acid (VPBA) -co-pentaerythritol triacrylate (PETA)) monolithic column was prepared by thermal-initiated copolymerization of VPBA and PETA in a binary porogen system comprising diethylene glycol and ethylene glycol. The fabricated monolithic column demonstrated good boronate affinity property, which can specifically capture cis-diols containing compounds. We developed such a monolithic column and applied it to enrich active components in Herba Taraxaci and Euonymus acanthocarpus. The extracts of the two traditional Chinese medicines were separated and enriched on microHPLC by the prepared monolith, and the fractions were collected and examined by HPLC. The results showed that the responses of the corresponding peaks were greatly improved, indicating that the poly( VPBA-co-PETA) monolithic column can be efficiently used to enrich active components in traditional Chinese medicines containing cis-diols group.