Six novel binuclear complexes have been reported in this paper: [Ln(2‐Cl‐6‐FBA)2(5,5′‐DM‐2,2′‐bipy)(NO3)]2, (Ln = Nd(1), Pr(2)); [Ln(2‐Cl‐6‐FBA)3(5,5′‐DM‐2,2′‐bipy)(H2O)]2, (Ln = Gd(3), Er(4), Eu(5), Ho(6); 2‐Cl‐6‐FBA = 2‐chloro‐6‐fluorobenzoate; 5,5′‐DM‐2,2′‐bipy = 5,5′‐dimethyl‐2,2′‐bipyridine). The complexes underwent comprehensive characterization, incorporating both elemental analysis and X‐ray diffraction (XRD) methodologies. The subsequent X‐ray single‐crystal structure diffraction analysis illuminated the existence of diverse coordination characteristics within these complexes: the coordination number of complexes 1 and 2 is 9, and the coordination number of complexes 3–6 is 8. The fluorescence spectra of complex 5 were obtained by fluorescence test. The detailed decomposition processes of the six complexes were studied by TG‐DTG‐DSC/FTIR technique. The nonisothermal kinetics of complex 6 at the third step were discussed by using M. J. Starink method, NL‐INT method, and double equal‐double step method.