Deuterium-labeled polyols were one of the most extensive applications in biochemistry and biophysics. However, the deuteriation reaction still exhibit low deuteriation rate and indistinct reaction mechanism. In this paper, Ru supported on MnBDC (derived from Mn-MOF) nano-catalyst, with agglomerated sheet-type structure, which ensure that possibility of achieving both thermo- and electro-catalytic hydrogen isotope exchange (HIE) reaction. Furthermore, XPS characterization affirmed that the specific structural changes in the electron density of Ru outer layers were modulated through the impregnation and reduction processes. According to the change of outer electronic structure, hydrogen spillover and electron-rich flow promote the reaction of catalyst in thermo- and electro-catalytic systems respectively. And, the results indicate that high deuterium rates of 97% can be obtained, which the catalytic technology has enormous potential for the synthesis of a broad variety of deuterium-labeled compounds.