NHC boryl radical mediated halogen atom transfer (XAT) is useful in organic synthesis. Yet, most of the reaction ends only with reducing the halogen to hydrogen, that is, the C-X to C-H. This is especially dominant for electron-deficient alkyl halides, where the formed electrophilic radical reacts rapidly with NHC boranes. Herein, by employing a sterically hindered NHC borane as the boryl radical precursor (IPr·BH 3 ), we were able to use the electrophilic-deficient alkyl halide (α-Iodide gem -di(B(pin))methane) in the C-C bond formation reaction. Mono-, disubstituted styrene, aliphatic alkenes, and heteroatom-substituted alkenes were used as reaction partners. Forty hydro( gem -diboryl)methylation products were obtained at room temperature in moderate to good yields. Detailed mechanistic studies revealed that the reaction mainly involved the radical process.