Poly(divinylbenzene-co-diethyene glycol dimethacrylate) [P(DVB-DGD)] microspheres were prepared by precipitation polymerization in acetonitrile solvent with divinylbenzene-55 and diethyene glycol dimethacrylate as comonomers. FTIR、SEM and BET were applied to characterize P(DVB-DGD). FT-IR showed that two monomers copolymerized during the precipitation polymerization process. SEM indicated that no macroporous structure could be observed and the average number diameter of the monodisperese microspheres was 3.6 μm. The surface area and the average diameter of P(DVB-DGD) were 2.9 m2/g and 9.1 nm, respectively. With two samples as probes, the chromatographic performance of novel stationary phase packed with P(DVB-DGD) was evaluated by reversed-phase liquid chromatographic mode. The chromatographic results showed that the peak shape of the analytes was sharp and symmetry. The column exhibited high column efficiency and excellent chromatographic performance,which indicated that precipitation polymerization showed great potency of stationary phase used in HPLC.