The polystyrene-supported CuI-imidazole complex catalyst was prepared and characterized by IR spectroscopy, elemental analysis, SEM/TEM and TG/DSC. The complex catalyst was globular with the size of 400-500 nm and showed a good thermal stability at high temperature. The immobilized Cu metal in the complex catalyst was about 0.85 mmol/g. By using the catalyst, aza-Michael reaction of imidazoles to alpha,beta-unsaturated compounds was performed with good yields in 4-8 h. The catalyst showed an excellent recycling efficiency over five cycles without distinct leaching of metal from the polymer support. (C) 2011 Elsevier B.V. All rights reserved.