A single-stage swelling and polymerization method was proposed for the synthesis of monodisperse porous poly(vinyl acetate-co-divinylbenzene) [poly(VAc-co-DVB)] particles with different VAc/DVB feed ratios. The particles obtained with the VAc/DVB feed ratio of 50:50 v/v had a narrow pore size distribution exhibiting a sharp peak at 30 nm. Based on this distribution the mean pore size and the specific volume were determined as 12 nm and 1.39 mL/g, respectively. The specific surface area of poly(VAc-co-DVB) particles was found to be 470 m(2)/g. These properties make poly(VAc-co-DVB) particles a promising support for potential HPLC applications. Poly(vinyl alcohol-co-divinylbenzene) [poly(VA-co-DVB)] particles were then obtained by the basic hydrolysis of poly(VAc-co-DVB) particles. The hydroxyl groups on poly(VA-co-DVB) particles have a suitably reactive functionality for surface grafting or derivatization protocols aiming at synthesizing various HPLC packings. The examination of poly(VA-co-DVB) particles by confocal laser scanning microscopy showed the homogeneous distribution of hydroxyl functionality in the particle interior. As a starting point, the chromatographic performance of plain material, poly(VAc-co-DVB) particles produced with VAc/DVB feed ratio of 50:50 (v/v) was tested by a commonly utilized chromatographic mode, reversed phase chromatography. Poly(VAc-co-DVB) particles were successfully used as packing material in the RP separation of alkylbenzenes with resolutions higher than 1.5. Theoretical plate numbers up to 17 500 plates/m were achieved. No significant change both in the chromatographic resolution and column efficiency was observed with increasing flow rate. The chromatography showed that poly(VAc-co-DVB) particles were a suitable starting material for the synthesis of chromatographic packings for different modes of HPLC.