Catalytic valorization of furfural (FUR) using a simple and low-cost metal catalyst has been considered as a hot topic in sustainable chemistry. In this work, a new Ni@R-Ca catalyst is prepared via the autocombustion and in situ reduction method. When it is employed to promote the catalytic valorization of FUR in aliphatic alcohol, a nearly complete FUR conversion with excellent product selectivity is obtained under mild reaction conditions. Using methanol as reaction medium, the sole product is furfuryl alcohol (FA) in which ca. 99% yield of FA was attained. While, in ethanol, the obtained products mainly contain FA and furan-2-acrolein (FUA) in which a 94% conversion of FUR with a 91% total selectivity of FA and FUA was acquired. Based on the characterization of catalyst including XRD, SEM, XPS and H2-TPR techniques, it is concluded that the synergy effect of metal Ni and R-Ca crystal lattice plays a crucial role in the efficient conversion of FUR in aliphatic alcohol.