Using sodium 1,4?dihydroxybenzene?2?sulfonate sodium (NaH₂L), 4,4'?bipyridine (bipy), Co(NO₃)₂·6H₂O and NiSO₄·6H₂O as raw materials, two mononuclear complexes containing nitrogen?donor ligands with similar structures, M(bipy)(H₂O)₄·(2H₂L)·4H₂O（M=Co（1）， Ni（2））, were synthesized by heating reflux method. The molecular structurse and composition were determined by single crystal X?ray diffraction, elemental analyses and thermogravimetric analyses. Co²⁺ and Ni²⁺ are six?coordinated, showing octahedral configuration, which are binded with one bipy molecule and four water molecules. H₂L^- anion does not coordinate with metal ions, balancing charges. In the complexes, H₂L^- anions, free water molecules and [M(bipy)(H₂O)₄]²⁺ cations can generate hydrogen bonds, which can form a network structure and increase the stability of the complexes. The fluorescence studies indicate that the maximum emission peaks of complexes 1 and 2 were 380 nm and 390 nm, respectively, which are characteristic fluorescence emission peaks of NaH₂L. The red shifts of the fluorescence emission peaks were due to the charge transfers between metal and ligand.