Two new bearing Bi(III) supramolecular compounds [Bi(pydcH)₃(Bi(pydcH)(pydcH₂)(pydc) (Bi(pydcH)(pydcH₂)(pydc)] (1) and {[Bi(pydcH)₃]·(H₂O)₅(Dmap)}₂ (2) have been successfully synthesized via hydrothermal reaction (pydcH₂ = 2,6-pyridine dicarboxylate, Dmap = 4-dimethylamiopyridine). They have been structurally determined by single-crystal X-ray analysis, and characterized by fluorescence analysis and thermogravimetric analysis (TG). Both compounds 1 and 2 are of the same triclinic system with different structures. The decomposition mechanisms of compounds 1 and 2 are discussed. Compared to 1, lots of small molecules were possibly removed from compound 2 below 250℃. In addition, the photoluminescence properties were also investigated.