Metal-free direct C–H functionalization reactions are a promising approach to convert hydrocarbon feedstock into value-added molecules. Diacetoxyl iodobenzene (DIB) is a benchtop stable hypervalent iodine compound that is frequently used as a non-metal oxidant in C–H functionalization. However, DIB has a relatively low reactivity and an acid promoter is usually required to achieve satisfactory performance. Herein, we report the use of a DIB/BBr₃ protocol for metal-free C(sp²)–H activation/cross-coupling of arenes.