An efficient method for the N-2-deoxyribosylation of modified nucleobases by 2-deoxythioriboside donors is reported. In the presence of an in situ silylated nucleobase, thioglycosides can be activated with NIS/HOTf to give nucleosides in high yields and with good β-selectivity. By tuning the protecting groups on the C3 and C5 hydroxyls, α/β ratios ranging from 1.0:4.0 to 4.5:1.0 can be obtained. This strategy is applicable to the synthesis of various nucleosides, including ring-expanded pyrimidine derivatives containing sulfur that have previously been reported in low yields. The utility of this approach is further demonstrated by the synthesis of fluorescent nucleosides analogues such as quinazoline and oxophenothiazine that should find broad utility in DNA-folding and recognition studies.