Using 1,2,3,5-benzenetetracarboxylic acid and different pyridyl ligands, three metalorganic coordination compounds, [Co(H ₃btec)(1,10-phen)(H ₂O) ₃][OH]·2H ₂O (1), [Co ₂ (btec)(2,2’-bipy) ₂-(H ₂O)]·H ₂O (2), {[Co ₁.₅ (H ₂btec)(4,4’-bipy)(H ₂O) ₂][Co ₀.₅ (4,4’-bipy)- (H ₂O) ₄][OH] ₂} · 2H ₂O (3), (H ₄btec = 1, 2, 3, 5-benzenetetracarboxylic acid, 1,10-phen = 1,10-phenanthroline, 2,2’-bipy = 2,2_-bipyridine, 4,4’-bipy= 4,4_ -bipyridine) were synthesized by hydrothermal method and characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. X-ray crystallographic studies reveal that 1 is a discrete 0D coordination compound, while 2 and 3 possess similar 2D network structures, which show a sql network with the point symbol of (4,4). Thermal analysis indicates that compounds 1 and 2 begin to collapse after 350◦C. Further, the UV-Vis DRS spectra and solid-state luminescent properties of 1–3 have also been studied.