Amine-functionalized mesoporous silica-supported copper catalysts SBA-15@amine–Cu and SBA-15@Oamine–Cu were prepared and proved to be efficient and reusable for homocoupling of terminal alkynes at room temperature with air as the oxidant. SBA-15@amine–Cu exhibited better recyclability than SBA-15@Oamine–Cu. The differences in the catalytic performances of the catalysts could be ascribed to catalyst structure and the interaction between copper and the supports. The as-prepared catalysts were systematically characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), high resolution-transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and nitrogen physical adsorption. The analysis indicated that the mesoporous structure of the materials was retained during the immobilization process. XPS results suggested that the as-prepared catalysts were not obtained by a simple physical adsorption of CuCl on the supports. It is noted that, for aliphatic alkynes, the catalytic activity of SBA-15@amine–Cu is even higher than that of the homogeneous copper catalytic system and that of some previously reported heterogeneous systems.