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The proton-conducting performances of a microporous Ti-based metal–organic framework (MOF), MIP-207, were successfully tuned using a multicomponent ligand replacement strategy to gradually introduce a controlled amount of sulfonic acid groups as a source of Brönsted acidic sites while keeping the robustness and ecofriendly synthesis conditions of the starting material. Typically, multivariate sulfonic-based solids MIP-207-(SO3H-IPA) x -(BTC)1–x were prepared by combining various ratios of trimesate 1,3,5-benzenetricarboxylate (BTC) moieties and 5-SO3H-isophthalate (SO3H-IPA). The best sulfonic-MOF candidate that combines structural integrity with high proton conductivity values (e.g., σ = 2.6 × 10–2 S cm–1 at 363 K/95% relative humidity) was further investigated using ab initio molecular dynamics simulations. These calculations supported that the −SO3H groups act as proton donors and revealed that the proton transfer mechanism results from the solvation structure of protons through the fast Zundel/hydronium interconversion along the continuous H-bonded network connecting the adsorbed water molecules.