Catalyzed by silver salt, the unactivated C(sp3)-H heteroarylation of free alcohol at the δ position is realized under gentle thermal conditions in water through a radical procedure. Both protonic acids and Lewis acids are found to be efficient for activating pyridines for this Minisci-type reaction. The reaction enjoys a good functional group tolerance and substrate scope. Terminal secondary and tertiary alcohols are suitable substrates. With either electron-donating or -withdrawing groups, the electron-deficient heteroarene substrates generate the target products in moderate to good yields. A gram-scale experiment can be successfully operated. A radical blocking experiment and a radical clock experiment are studied to support the radical mechanism.