A highly efficient heterogeneous copper-catalyzed chlorodeboronation of arylboronic acids with inexpensive N-chlorosuccinimide (NCS) was achieved in MeCN in the presence of 10 mol% of L-proline-functionalized MCM-41-immobilized copper(I) complex [MCM-41-L-proline-CuCl] under mild conditions, yielding a variety of aryl chlorides in excellent yields. This method proved to be tolerant of a broad range of functional groups and particularly useful for the conversion of electron-deficient arylboronic acids to aryl chlorides, a transformation that is inefficient without copper catalysis. This heterogeneous copper catalyst can be recovered by a simple filtration of the reaction solution and recycled for at least 10 times without any decreases in activity.