Facile chemical approaches for the controllable synthesis of CuSe, CuInSe2 nanowire, and CuInSe2/CuInS2 core/shell nanocable bundles were developed. Hexagonal CuSe nanowire bundles with lengths up to hundreds of micrometers, consisting of many aligned nanowires with a diameter of about 10-15 nm, were prepared by reacting cubic Cu(2-x)Se nanowire bundles with a sodium citrate solution at room temperature. The CuSe nanowire bundles were then used as self-sacrificial templates for making bundles of tetragonal chalcopyrite CuInSe2 nanowires by reacting with InCl3 via a solvothermal process. Furthermore, bundles of CuInSe2/CuInS2 core/shell nanocables were obtained by adding sulfur to the reaction system, and the shell thickness of the polycrystalline CuInS2 in the nanocables increased with increasing S/Se molar ratios. It was found that the small radius of copper ions allows their fast outward diffusion from the interior to the surface of nanowires to react with sulfur atoms/anions and indium ions to form a CuInS2 shell. Enhanced optical absorption in the vis-NIR region of CuInSe2/CuInS2 core/shell nanocable bundles is demonstrated, which is considered beneficial for applications in optoelectronic devices and solar energy conversion.