Development of a high-efficiency heterogeneous catalyst for modern organic synthesis is greatly important. Herein, a nanosized ETS-10 zeolite (ETS-10-N) with strong Lewis basicity was synthesized, and used as support for prepared Cu catalyst (Cu/ETS-10-N) showing superior catalytic activity and selectivity in the decarboxylative cross-coupling of cinnamic acid and tetrahydrofuran, as compared to acidic mesoporous Beta and conventional bulk ETS-10 zeolite supported Cu catalysts. The strong Lewis basic site in the Cu/ETS-10-N not only could facilitate the formation of the alkyl radical transformed from tetrahydrofuran, but also could favor the chemisorption of cinnamic acid and activate the carbon-carbon double bond, enhancing the catalyst activity. Additionally, the Cu2+ and Cu+ species in the Cu/ETS-10-N could coordinated with the carboxylate oxygen atoms derived from cinnamic acid, improving the reaction activity of the substrate.