The decarboxylative coupling of cinnamic acids with alcohols and the oxidative coupling of alkenes with aldehydes are typical organic reactions. Considering the characteristics and mechanisms of the reactions, the Cu-doped zeolite-X catalyst (Cu-X) with Lewis basic sites was synthesized and used for the two reactions. Compared with Cu, Cu2O, and CuBr2 catalysts (4–21%), the Cu-X catalyst (99%) shows extraordinary high activity in the decarboxylative coupling of cinnamic acids with alcohols. In addition, the Cu-X catalyst presents excellent performance in the oxidative coupling of alkenes with aldehydes. The strong interaction between Cu+ and the zeolite framework benefits the transformation of Cu2+ and Cu+ in the redox process, enhancing the reaction activity. More importantly, the Lewis basic sites on the Cu-X catalyst could favor the adsorption of the cinnamic acid, resulting in electron-rich density in the CC bond, and therefore greatly improving the reaction activity.