Abstract: The investigation of the coordination chemistry of actinides/lanthanides is very instructive for the operation control of actinides/lanthanides in spent fuel reprocessing, the designs of new extractants/stripping agents, depicting and controlling the migration of long-lived actinides in environment, and reducing the toxicity of actinides in organisms. Versatile spectroscopic method is the important method to provide thermodynamic information and reveal structural details of Ln/An complexes, such as the coordination modes, bond length and angle in the coordinated complexes. The present paper briefly reviewed the application of spectroscopic techniques which were frequently used in recent years for studying actinides/lanthanides complexation, especially focusing on the application of fluorescence and Raman spectroscopy in the determination of thermodynamic parameters and structural analysis of actinides complexes. Furthermore, the application of integrated spectroscopic methods in the study of actinide/lanthanide coordination chemistry was valuated to be more informative and instructive.