By introducing a bis-pyrazole-bis-amide ligand, N,N′-bis(1H-pyrazole-4-carboxamide)-1,4-benzene (L), two molybdate-based metal–organic complexes containing {M₂(MoO₄)₂}_n (M = Co, Zn), [Co₂L₂(MoO₄)₂]·H₂O (1), [Zn₂L₂(MoO₄)₂]·H₂O (2), have been prepared under hydrothermal/solvothermal conditions. X-ray diffraction analyses reveal that both 1 and 2 are isostructural. An interesting structural feature is that a kind of {M₂(MoO₄)₂}_n chain could be found in 1 and 2, although different raw materials [Mo₇O₂₄]⁶⁻ and [PMo₁₂O₄₀]³⁻ anions were utilized. Then these chains are further linked by L ligands into a two dimensional (2D) structure. The title complexes represent the first examples containing {MoO₄} units and pyrazole-/or amide-derivative ligands. Complexes 1 and 2 exhibit distinct performances due to different metal centers, with 2 acting as a fluorescent sensor for Fe³⁺, MnO₄⁻, CrO₄²⁻ and Cr₂O₇²⁻, but 1 being a better photocatalyst towards degradation of cationic dyes methylene blue (MB) and neutral red (NR).