A one-step procedure to hydrophilize monodisperse poly (chloromethyl-styrene-co-divinylbenzene) beads has been presented with 2-hydroxy-3-[4-(hydroxymethyl)-1H-l,2,3-triazol-l-yl] propyl 2-methylacrylate (HTMA) as monomer by surface-initiated atom transfer radical polymerization (SI-ATRP). The length of the grafted poly (HTMA) chain was varied via controlling the ratio of HTMA to initiator on the surface of the beads. Using these grafted beads as the stationary phase in hydrophilic interaction chromatography, good separation was obtained for nucleosides in the mobile phase of acetonitrile-water. It was also found that the retention time and selectivity of solutes showed a positive relationship with the length of the grafted poly (HTMA) chain.