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A facile citric acid-mediated complexation-calcination approach is reported in this paper to prepare the CeCu oxide composite with a porous structure that is highly efficient and durable for treating simulated quinoline wastewater by catalytic wet hydrogen peroxide oxidation (CWPO). As the results indicate, Cu species can be dissolved in CeO2 lattice to fabricate a solid solution. The calcination temperature is critical for an optimum catalyst structure and catalytic performance. As found in investigating the structure and catalytic performance of the CeCu oxide prepared at calcination temperatures ranging from 350 to 750 ºC, the optimum temperature is 650 ºC, at which a loose surface, a porous structure and considerable adsorbed surface oxide/hydroxyl oxide species are fabricated over the catalyst. This resultant catalyst also takes on the optimal performance with an oxidation conversion reaching 98% for quinoline, a removal efficiency of 80.6% for total organic carbon (TOC) and a low Cu2+ leaching value of 19.3 mg L-1. Besides, the high performance is maintained by the catalysts in a wide pH range of 5.1-10.5. This work generally provides an efficient way to design and fabricate the catalyst for CWPO reaction, which can also be applied in other reactions.