Two new 3D framework materials containing Bi₂O₂ layers and Bi₄O₃ chains have been obtained hydrothermally via the reactions between bismuth nitrate with terephthalic acid (TA) and bismuth nitrate with nitro-terephthalic acid (NO₂TA), respectively. The Bi₂O₂ layers are connected into a 3D structure via bridging TA ligands to form Bi₂O₂(TA) (1), while the novel Bi₄O₃ chains are connected into a 3D framework via linking NO₂TA ligands to form Bi₄O₃(NO₂TA)₃(H₂O)·(H₂O)_0.68 (2). Compound 1 exhibits photoluminescence that is red-shifted compared to that of the TA ligand, while the photoluminescence is quenched in both compound 2 and the NO₂TA ligand.