The Coulomb force between protons and negative charges usually leads to low proton diffusion and poor proton conductivity. Herein, acid-base conjugated MOFs of UiO-66-SO 3 - -NH 3 + were constructed by linking sulfonic acid and amine groups to an organic skeleton. According to the XPS and elemental analysis, the ratio of 2-aminoterephthalic acid/2-sulfoterephthalic acid was ∼1.9 in UiO-66-SO 3 - -NH 3 + . After introducing sulphuric acid molecules, the MOF-based electrolyte exhibited a remarkable proton conductivity of 5.40 × 10 -1 S cm -1 and low activation energy of 0.15 eV at 100% RH and 90 °C. This remarkable proton conducting behavior was generated by the synergistic system in the MOF, which contained certain synergistic effects such as between -SO 3 - ⋯H + ⋯SO 4 2- and NH 3 + ⋯SO 4 2- , therefore possessing a Grotthuss mechanism, which facilitates facile proton transport.