Valence engineering of copper (Cu) within functional materials is effective to tune the performance and energetics of catalysts and sorbents. Here, by precisely controlling the Cu(II)/Cu(I) ratio employing Na2S2O3 as the reduction agent, we synthesized a family of copper-1,3,5-benzenetricarboxylic acid (Cu-BTC) sorbents for organosulfur compound capture. Integrated X-ray absorption fine structure and density functional theory studies suggest that the atomic-level, short-range order changes caused by Cu reduction lead to simultaneous stability, affinity, and pore topology evolutions in Cu(I)/Cu(II)-BTC, which govern the sorption capacity and binding energetics of dimethyl disulfide capture. This multiscale fundamental study with both experimental and computational results highlights the power of coordination chemistry on materials engineering on atomic level.