The catalytic performance of heterogeneous catalysts remains a great challenge for large-scale commercial applications under harsh reaction conditions. Herein, we designed a CuNiAl catalyst using a layered double hydroxides precursor, and the catalytic performances were evaluated in transfer hydrogenation of levulinic acid to γ-valerolactone with formic acid as a hydrogen donor. CuNiAl catalyst presented high activity and the improved stability compared to CuAl catalyst. The CuNi alloy formed in the CuNiAl catalyst could prevent Cu particles from partial oxidation, overgrowth and leaching under acidic reaction conditions. Moreover, the synergistic effects between Cu active sites and the surface acid-base on the surface were the key factors for producing γ-valerolactone with a high yield of 97.3% over the CuNiAl catalyst.