The catalytic transformation of the most abundant cellulose to valuable platform chemicals is one of the significant issues to overcome the shortage of fossil fuels. Herein, we reported the first example of Ru-based homogeneous catalyst-for the highly selective conversion of cellobiose and ball-milled cellulose to hexitols (including sorbitol, mannitol, and 1,4-sorbitan) under an acidic condition with the yield of 94.5% and 56.4%, respectively. The main features of this catalytic system were the high conversion efficiency of biomass, mild reaction condition (100 degrees C), and low catalyst loading, which was 1/20 of the related Ru/C heterogeneous catalyst. This work opened up a new avenue for the transformation of cellulose to hexitols under mild conditions.