Porous poly(vinyl ester) resin monolithic supports were first prepared by radical polymerization of the continuous phase of oil in water high-internal-phase emulsions. Vinyl ester (VE) resin was used as the monomer, ethylene glycol dimethacrylate was used as a crosslinker, and poloxamer 127 was used as the emulsifier in the emulsion polymerization. The prepared columns were evaluated by scanning electron microscopy, mercury intrusion porosimetry, and Fourier transform infrared spectroscopy to observe the morphological characteristics and confirm the absorbance based on the VE resin polymer. The obtained monolith showed not only higher column permeability but also lower back pressure and higher column efficiency. To investigate the absorption performance of the monolithic column, a maximum loading capacity experiment was also applied with lysozyme (Lys), and the results show that the maximum adsorption of the poly(vinyl ester) resin monolith was 1.579 mg/g. Moreover, the capabilities of separation on this column in conjunction with high-performance liquid chromatography were investigated. Immunoglobulin could be separated from human plasma and chicken egg yolk with high resolution within 4 min. Additionally, fast separation of two mode proteins (interleukin-18 and Lys) was achieved on the monolith within 2 min at the rate of 1445 cm/h, which demonstrated the potential of the poly(vinyl ester) resin monolith for the fast separation of proteins. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 412-418, 2011