Two novel complexes, namely ［Co(L′)3］ (1) and ［Cu(L′)2］n (2) (HL′=5-bromopyridine-2-carboxylic acid), were obtained under solvothermal conditions by the assembly process of organic carboxylate ligand containing halogen (3-bromopyridine-2,6-dicarboxylic acid, H2L) and Co(NO3)2·6H2O or Cu(NO3)2·3H2O respectively, and characterized by element analysis (EA), X-ray single diffraction (SXRD), X-ray powder diffraction (PXRD), infrared spectroscopy (IR) and thermogravimetric analysis (TGA). The single crystal X-ray diffraction reveals that ligand H2L transform to HL′ during a decarboxylation process. In the asymmetric unit of 1, there are two mononuclear units. In each unit, central Co(Ⅲ) ion is in a slightly distorted octahedron. Complex 1 shows mononuclear structure, forming a three-dimensional (3D) supramolecular structure via C-H…O hydrogen bonding interactions. The asymmetric unit of 2 contains one central Cu atom and two L′- ligands. In each unit, central Cu(Ⅱ) ion is in a slightly distorted octahedron. Complex 2 exhibits 1D chain structure, forming a three-dimensional (3D) supramolecular structure via C-H…O hydrogen bonding interactions. Furthermore, the stability property of complexes 1 and 2 was also investigated.