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To systematically explore the effects of polynuclear complexes on the removal of chromium pollutants, a new three-dimensional (3D) microporous metal-organic compound [Cd 3 (HCO 2) 2 (dpa) 4 (bpp) 3 ] n (dpa ​= ​diphenic acid, bpp ​= ​1,3-bi(4-pyridyl)propane) (1) was prepared through hydrothermal synthesis. The structure was characterized by X-ray single crystal diffraction, elemental analysis, and Fourier transform infrared spectroscopy. The results indicate that complex 1 based on Cd(II) clusters is monoclinic and consists of the C 2/ c space group. It exhibits a new 2-nodal (3,5)-connected 3D framework with a Schläfli symbol of {43}{45, 65}. The thermogravimetric analysis (TGA) reveals complex 1 has high thermal stability (stable until 490 ​°C). The photoluminescence shows the emission wavelength of the fluorescence is red-shifted (30 ​nm), and the intensity is significantly increased compared to the free ligand. Adsorption analysis shows that the Cd(II) compound demonstrates significant adsorption towards the dichromate anion (Cr 2 O 7 2−). Its adsorption isotherm is consistent with the Langmuir model and its adsorption kinetics follows a pseudo-second-order model. 3D polynuclear Cd(II) complexes exhibit photo-fluorescent property and adsorption towards the dichromate anion. Image 1 • A new polynuclear coordination polymer [Cd 3 (HCO 2) 2 (dpa) 4 (bpp) 3 ] n has been prepared and characterized. • Cd(II) clusters with 1D+2D→3D framework and a new 2-nodal (3,5)-connected topology. • Robust microporous 1D channel for dichromate removal in an aqueous solution. [ABSTRACT FROM AUTHOR]