Pentanediols (1,2-pentanediol and 1,5-pentanediol) are important feedstock for synthesis of fine chemicals, production of which from the biomass-derived furfural or furfuryl alcohol (FA) has been considered as a sustainable route and attracted much interest. In this study, the catalysts with Ni-Fe as the metal sites and Mg-Al layered double hydroxides (LDH) as precursor of support were synthesized. The results showed that the presence of Fe in catalyst affected both the development of the pores of the catalyst and the catalytic behaviors of nickel species. A low Fe content facilitated formation of meso-porous structure, but the higher content destroyed the LDH structure, resulting in a decreased surface area. Fe could also react with metallic Ni to form NiFe alloy. This decreased the catalytic activity for the further hydrogenation of the furan ring in FA, and FA would thus have the chance to produce penta-nediols via hydrogenolysis. The In-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy characterization of hydrogenation of FA indicated that the alloying between Fe and Ni resulted in a weak adsorption of C=C group in furan ring and moderate adsorption of C-O-C group, which suppressed the complete hydrogenation of FA while facilitated the ring-opening of FA to form the pentanediols. ? 2021 Elsevier Ltd. All rights reserved.