An efficient and convenient method for the synthesis of C3-hydroxytrifluoroalkylated indoles and pyrroles was described in this paper. The copper-catalyst-free site-specific cross-dehydrogenative coupling reaction of various indoles and pyrroles with hexafluoroisopropanol proceeded smoothly by using MnO 2 as oxidant to furnish a hydroxytrifluoroalkylated electron-rich Nheterocycle in satisfactory to excellent yields. Various groups, including the synthetically useful functional groups Cl, NO 2 , and CN, were tolerated well. The mechanistic study revealed that a radical pathway accommodated the formation of a hexafluoroacetone intermediate.