5-(Chloromethyl)furfural (CMF), as a new platform molecular, has become a hot topic in the field of biorefinery. Herein, the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan (BHMF) in the water phase was demonstrated for the first time. A 91% BHMF yield was obtained over Ru/CuOx catalyst, and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural (HMF) as an intermediate. Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step. Remarkably, the characterizations and density functional theory (DFT) calculations further revealed the lower electron density of Ru NPs in Ru/CuOx catalyst, resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols. The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.