A-site Ce substituted and B-site Rh doped reduced perovskites were successfully prepared and used as active, selective and leaching-resistant catalsts for xylose aqueous-phase hydrogenation. In the A-site the 6 wt.% La substituted by Ce decreased the crystallinity and increased the surface area and thermal stability in reductive atmosphere whereas large decreases in the surface area, and an easier reduction of nickel was detected in the 0.3 wt% Rh doped B-site perovskites. An increase in the conversion level upon Ce substitution and an enhancement of the selectivity to xylitol in the Rh doped reduced perovskites is reported. The highest catalytic performance and xylitol selectivity of the Ce-substituted and Rh doped Ni reduced catalyst was attributed to the XRD detected Ni particle size. All catalysts showed activity in the aqueous-phase hydrogenation of xylose, and in contrast with other Ni catalysts, the reduced perovskite catalyst showed to be Ni leaching resistant at all over 6 h of reaction. (C) 2017 Elsevier B.V. All rights reserved.