Reducing catalyst costs and reaction energy consumption is a potent way to advance biorefinery energy from fundamental research to industrial implementation. Herein, we developed a series of low-cost CuCo/Al2O3 catalysts for hydrodeoxygenation of 5-hydroxymethylfurfural to biofuel 2,5-dimethylfuran (DMF). Combined characterizations showed CuCo alloy and Co@CuCo core-shell structures were successfully constructed by reducing layered double hydroxides (LDHs) at different temperatures. Detailed catalytic performance studies found that Co@CuCo catalyst achieved a decent DMF yield of 91.7% under 130 oC and 1MPa H2, which is milder than most literatures. While the CuCo alloy catalyst only gave 23.2% yield. H2-TPD and In-situ-IR indicated the CuCo-alloy shell can prevent oxidation of Co core, so that maintain its high H2 dissociation capacity. Moreover, the electronic structure changes in the Cu-Co alloy promote the hydrolysis of C-O bond. Hence, the local atomic arrangement and corresponding electronic structure in the Co@CuCo structure jointly strengthened the low-temperature reactivity.