A preparative method of Me2SCuX (X = Cl, Br) via one-pot reaction was developed from common chemicals such as benzyl halide, DMSO, and Cu(0). In the reaction mixture small molecules such as methyl halide and dimethyl sulfide etc. were efficiently generated in situ, resulting in the formation of Me2SCuX. Oxidation of Cu(0) in reacting with both benzyl halide (starting material) and methyl halide (in situ generated product) to Cu(I) followed by complexing with dimethyl sulfide (in situ generated product) could explain the formation of Me2SCuX. In particular we found out that heterogeneous reaction of Me2SCuX and arenediazonium tetrafluoroborate in acetonitrile was so effective to afford corresponding bromoaromatics under mild conditions.