1,3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranose and 1,3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-beta-D-galactopyranose reacted with protected nucleosides in the presence of BF(3) as promoter at room temperature to give selectively 2-amino-2-deoxy-beta-glycosyl (1-->5)nucleosides in good yields. CD spectra and thermal melting studies showed that 2-amino-2-deoxy-beta-D-glucopyranosyl-(1-->5)-nucleosides could interact with RNA in solution and 2-deoxy-2-amino-beta-D-galactopyranosyl-(1-->5)-nucleosides (17-19) exhibit higher affinity to RNA than 2-deoxy-2-amino-beta-D-glucopyranosyl-(1-->5)-nucleosides (14-16). It indicated that the majority of interactions are established between the polar group of glycosylnucleosides and the sugar-phosphate backbone of RNA helices and weak stacking interaction is observed. The different configuration of hydroxyl group on the glycosyl moiety may affect the glycosyl-nucleoside binding to RNA by induced fit.