Ni-catalyzed Sonogashira coupling of nonactivated, B-H-containing alkyl halides, including chlorides, is reported. The coupling is tolerant to a wide range of functional groups, including ether, ester, amide, nitrite, keto, heterocycle, acetal, and aryl halide, in both coupling partners. The coupling can be selective for a specific C-X bond (X = 1, Br, Cl) and allows for orthogonal functionalization of alkyl halides with multiple reactive sites.