The highly regioselective C 6 -H hydroxylalkylation of purines and purine nucleosides within 10 min via the α-C(sp 3 )-H functionalization of alcohols at room temperature is reported here for the first time. The reaction tolerated various functional groups, which have the potential for further modification to afford other valuable molecules. The reported method avoids metal catalysts, light, and protecting groups, giving a direct strategy to access 6-substitued alkylated purines and nucleosides with pharmaceutical bioactivities.