In the face of the continuous consumption of fossil energy and the increasingly serious ecological damage, the synthesis of liquid fuels and high value-added fine chemicals from biomass-derived furfural has become one of the research hotspots in the field of energy and chemical industry. In this work, a highly efficient and selective aerobic oxidative condensation of furfural with straight-chain alcohol is achieved with simple copper(I) chloride as the catalyst. Therein, 3-(2- furanyl)-2-methyl-2-acrolein was synthesized by the oxidative condensation reaction of furfural with n-propanol under the mild conditions. As a result, it is found that the conversion of furfural and the selectivity of main product reached 94% and more than 99.9% in the presence of molecular oxygen, respectively. Moreover, the effects of basic additive, reaction time and temperature were further investigated in detail. In addition, oxidative condensation of different substrates was also successfully performed. This catalytic method provides a promising, green and sustainable technology for the valorization of biomass and biomass-based platform compounds.