The dual-functional metal phosphonate materials with excellent luminescence recognition and proton conduction are a research focus.Herein, two examples of three-dimensional (3D) transition metal phosphonate materials, namely [Cd2(L1)2(Bib)2(H2O)]·4·5H2O (Cd-MOF-1) and [Cd(L2)(Bib)]·3H2O (Cd-MOF-2), were synthesized by self-assembly with transition metal cadmium ions (CdII) under hydrothermal conditions using the isomeric phosphonic acid ligands, 4-carboxyphenylmethylphosphonate Et ester (H2L1) and 3-carboxyphenylmethylphosphonate Et ester (H2L2), and auxiliary ligand 1,4-bis-(1H-imidazol-1-yl)benzene (Bib).Both Cd-MOF-1 and Cd-MOF-2 act as fluorescent probes can achieve rapid, highly sensitive, highly selective and recyclable detection of benzophenone (BP) through fluorescence quenching in the water/ethanol (v: v = 1: 1) solution system.The luminescent recognition mechanisms were thoroughly investigated through experiments and d. functional theory (DFT) calculations, revealing the synergistic effect of static quenching, photo-induced electron transfer (PET), inner filter effect (IFE), and energy competitive absorption.In addition, research on the proton conductivity showed that, at 95 % relative humidity (RH) and 368 K, Cd-MOF-1 and Cd-MOF-2 exhibited proton conductivities of 3.51 x 10-5 S cm-1 and 1.21 x 10-5 S cm-1, resp.Activation energy (Ea) anal. indicated a Grotthuss (0.37 eV, 333 ∼ 353 K) and Vehicle (1.03 eV, 358 ∼ 368 K) mechanism for Cd-MOF-1, and a Grotthuss mechanism (0.18 eV, 333 ∼ 368 K) for Cd-MOF-2.Detailed structure-activity relationship studies demonstrated that effective active sites and hydrogen-bonding networks enhance the luminescent recognition and proton conductivity performances of the materials, which provided valuable references for the rational design and construction of dual-functional metal phosphonate materials.