A three-dimensional Bi(III) based metal–organic framework was synthesized under hydrothermal conditions using the multidentate organic linker 3,5-pyridinedicarboxylate. Bismuth oxide 3,5-pyridinedicarboxylate, Bi 2 O 2 [NC 5 H 3 (CO 2 ) 2 ], contains embedded 1-D cationic bismuth oxide chains that propagate along the crystallographic c-axis. The oxygens of the Bi 2 O 2 core are three-coordinate and bond strongly to the Bi atoms. Thermogravimetric analysis shows that the material possesses high thermal stability up ca. 400°C before decomposing to phase-pure Bi 2 O 3 at 800°C. The structure, crystallinity, morphology and properties of the material are discussed.