The catalytic activity of crystallites depends mainly upon the arrangement of surface atoms, the number of dangling bonds, and defect site distribution on different crystal planes. Here, we report the shape-controlled synthesis of CuCl crystallites, including tetrahedra, face-centered-etched tetrahedra, tripod dendrites, and tetrapods. These different morphologies of CuCl crystallites expose different proportions of {111} and {110} crystal planes, and materials with a preponderance of {111} crystal planes have better catalytic activity in aniline coupling than those with more {110} planes.