SBA-15-supported CuO was synthesized via wet impregnation of SBA-15 with copper (II) acetylacetonate followed by calcination in the static air. The BET surface area of the Cu-containing SBA-15 was approximately 600 m2/g, which significantly decreased in comparison with that of as-synthesized SBA-15 silica (1081 m2/g). The successful loading of copper with a 3.20 wt.% content was determined by ICP-OES analysis, consistent with theoretical composition. However, no Cu-based phases were detected on the PXRD results and TEM images for CuO/SBA-15 showed regular hexagonal meso channels remained, indicating that CuO species was well distributed in the SBA-15 framework via the applied synthetic procedure. Catalytic activity of SBA-15-supported CuO was investigated for the selective C(sp2)-O coupling reaction between salicylaldehyde and N, N-dimethylformamide (DMF) in the presence of di-tert butyl peroxide (DTBP) as an oxidant. Influence of the reaction conditions on the formation of desired product was studied including reaction time, temperature, reactant ratio, amount of catalyst and oxidant. The experimental results proved that the high activity of the prepared catalyst as the C(sp2)-O coupling product could be obtained in an excellent yield of 90% with only 3 mol% of SBA-15-supported CuO in the presence of 4 equivalents of DTBP at 120 °C in 2 hours.