A one-pot approach was used to convert polyethylene (PE) with different chain structures into carbon nanomaterials (CNMs) under the combined catalysis of CuBr and NiO at 700 degrees C, including linear low density polyethylene (LLDPE), low density polyethylene (LDPE) and high density polyethylene (HDPE). The effect of chain structure of PE on the yield, morphology, microstructure, phase structure and thermal stability of CNMs, including cup-stacked carbon nanotubes (CS-CNTs) and carbon nanofibers (CNFs), were investigated by scanning electron microscope, transmission electron microscope (TEM), high-resolution TEM, X-ray diffraction, Raman spectroscopy and thermal gravimetric analysis. In addition, the degradation products from different chain structures of PE under the catalysis of CuBr were analyzed by gas chromatography and gas chromatography-mass spectrometry. It was demonstrated that the branched structure played an important effect in the degradation products of PE. The dehydrogenation and aromatization of LLDPE were remarkably promoted by Br radicals from the decomposition of CuBr to form a large amount of light hydrocarbons and a relatively small amount of aromatics, favoring the formation of long and straight CS-CNTs. However, the degradation of LDPE was not obviously influenced by Br radicals due to its high extent of branched structure, while the random cleavage of HDPE was accelerated with the formation of a lot of olefins with long chains, resulting in the formation of short and winding CNFs. This work will contribute to the conversion of mixed waste polyolefin into high value-added CNMs. (C) 2013 Elsevier B.V. All rights reserved.