Three novel lanthanide complexes [Er (3,4‐DMBA)3(5,5′‐DM‐2,2′‐bipy)(H2O)] (1); [Tb2 (3,4‐DMBA)6(5,5′‐DM‐2,2′‐bipy)2(H2O)] (2); [Eu (3,4‐DMBA)3(3,4‐DMHBA)(5,5′‐DM‐2,2′‐bipy)]2 (3) (3,4‐DMHBA = 3,4‐dimethylbenzoic acid, 5,5′‐DM‐2,2′‐bipy =5,5′‐dimethyl‐2,2′‐bipyridine) were successfully synthesized via conventional solution method at room temperature and structurally characterized by single crystal diffraction. The structures of the complexes 1–3 were confirmed on the basis of elemental analysis, coordination titration analysis, IR and XRD. The molecular structures of complexes 2 and 3 are very particular: complex 2 has two same central metal ions but each metal ion has different coordination environment; in structure of the complex 3, there are eight carboxylic acid ligands coordinated to the central metal ions, which have rarely been reported previously. The thermal decomposition mechanism of complexes 1–3 were investigated by the technology of simultaneous TG/DSC‐FTIR. The heat capacities of the complexes were recorded by means of DSC over the range of from 253.15 K to 345.15 K. The thermodynamic parameters, the smoothed values of heat capacities, enthalpy (HT‐H298.15K) and entropy (ST‐S298.15K) were also calculated. The bacteriostatic activities of the complexes were evaluated against Staphylococcus aureus, Escherichia coli and Candida albicans. What's more, the luminescence properties of complexes 2 and 3 were discussed, and their fluorescence lifetimes as well as the quantum yield of the Eu (III) were measured. To elucidate the energy transfer process of complexes 2 and 3, the energy levels of the relevant electronic states have been estimated.