In this work, CuO modified Ce0.7Zr.O-03(2) (CZ) solid solution including CuO-deposited CZ (i.e., Cu/CZ) and doped CZ (i.e., Cu-CZ) are prepared. The correlation of CuO neighboring structure with the catalytic performance for NO reduction have been proposed by various spectroscopic technologies. Results suggested that the strong synergetic effect between surface deposited copper species and CZ support can easily promote the reducibility of Cu/CZ, which enhances its catalytic performance. In addition, the decomposition of NO occurs through different pathways over Cu/CZ and Cu-a, respectively, as suggested by in-situ FTIR results. The distinct chemical state and environment of copper species between Cu/CZ and Cu-CZ can account for these differences. A surface model and the reaction mechanism are proposed to discuss the differences showing in the catalysts. (C) 2017 Elsevier B.V. All rights reserved.