Three-dimensional iodoargentate hybrids [Co(en)₃(Ag₂I₄)]_n (1), [Fe(en)₃(Ag₂I₄)]_n (2) (en = ethylenediamine) and [Co(dien)₂(Ag₂I₄)]_n·nH₂O (3) (dien = diethylenetriamine) were prepared in C₂H₅OH solvent via a one-step reaction under solvothermal conditions. In compounds 1 and 2, AgI₄ tetrahedra were interlinked via corner-sharing to form a 3D α-Ag₂I₄ framework with interpenetrated channels with cross sectional dimensions of 8.071 Å × 9.039 Å and 9.039 Å × 9.039 Å. The AgI₄ tetrahedra in compound 3 were connected via both corner- and edge-sharing into a 3D β-Ag₂I₄ framework with dimensions of 5.929 Å × 8.329 Å, and 8.329 Å × 9.910 Å. Compounds 1–3 showed sensitive photocurrent response under visible light irradiation with steady current densities in the range of 3.46–8.26 μA cm⁻². These compounds were catalytically active during the photodegradation of crystal violet (CV), with degradation conversions of 72.2%, 91.5% and 80.1% after 105 min of light irradiation over compounds 1–3, respectively.