The investigation of complex formation between a bicyclic diamide, a novel chelating agent for lanthanides and actinides, and lutetium in an acetonitrile solution is reported. A free ligand and its lutetium complexes showed weak, noncharacteristic near-UV absorption and no fluorescence, which limited the application of absorption and fluorescence spectroscopies for studying this system. Deep-UV Raman spectroscopy combined with chemometric analysis was shown to be a powerful tool for quantitative characterization of multiple equilibria between lutetium and a bicyclic diamide. Several chemometric methods were utilized for a comparative analysis of Raman spectroscopic data. It was found that a recently developed stepwise maximum angle calculation algorithm followed by alternative least squares (ALS) was more efficient than the commonly used combination Of Evolving factor analysis and ALS methods, especially when little or no information about the system composition and the spectra of individual components was available. A free ligand and 1:1, 1:2, and 1:3 metal-ligand complexes were distinguished in a bicyclic diamide-lutetium solution. The composition evolution of the solution during the course of titration with lutetium was described, and the stepwise stability constants of complex formation, K-1:K-2 = 0.80 +/- 0.15 (K-1,K-2 > 10(8) M-1) and K-3 = (5.5 +/- 1) x 10(3) M-1, were estimated.