A europium(III) metal-organic framework (MOF), namely, {[[(CH3)2NH2]3Eu2(DTTP-2OH)2(HCOO)(H2O)]·4H2O}n (Eu-MOF, H4DTTP-2OH = 2',5'-dihydroxy-[1,1':4',1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid) has been assembled through solvothermal method. The Eu-MOF is a three-dimensional (3D) (4,4,8)-connected topological framework with binuclear Eu(III) clusters as secondary building units, in which a richly ordered hydrogen bonding network formed among the free H2O molecules, dimethylamine cations, and phenolic hydroxyl groups provides a potential pathway for proton conduction. The proton conductivity reaches the category of superionic conductors (σ > 10-4 S cm-1) at room temperature with a maximum conductivity of 1.91 × 10-3 S cm-1 at 60 °C and 98% RH. Moreover, it also can be used as a fluorescence sensor in aqueous solution with detection limits of 0.14 μM for tetracycline, 0.13 μM for oxytetracycline and 0.11 μM for doxycycline. These results pave new methods for constructing MOFs with high proton conductivity and responsive fluorescence.