A one-pot approach to prepare Cu-Ni/C heterogeneous composites by carbonization of polypropylene (PP) using combined catalysts of Ni2O3 and CuCl was proposed. TEM. SEM, TGA and Raman measurements were performed to investigate the effects of Cl/Ni molar ratios on the yield and morphology of the resultant carbon materials. The yield of carbon materials in Cu-Ni/C first increased and then decreased as the Cl/Ni molar ratio increased, and the maximum yield was achieved at Cl/Ni molar ratio of 0.125. Longer and thinner carbon nanotubes (CNTs) were obtained at low Cl/Ni ratios while shorter carbon fibers were formed at high CUM ratios. The effect of Cl/NI molar ratio on the active sites for the growth of carbon materials and degraded products of PP were investigated by XRD. GC and GC-MS. Interestingly, the resultant Cu-Ni/C showed the catalysis to "Click" reaction. As a result, the initial catalytic substances (Ni2O3 and CuCl) could be effectively used twice as catalysts in the carbonization of PP and in the later application of the resultant Cu-Ni/C composites. More importantly, this approach is a new potential method to transform waste polymer materials into valuable metal/carbon heterogeneous composites. (C) 2012 Elsevier B.V. All rights reserved.