Optical spectroscopic measurements in the UVVis and IR ranges were performed in model solutions of aqueous and organic phases of the PUREX process for spent nuclear fuel (SNF) reprocessing. Chemometric processing of the spectral data with PLS (partial least squares) regression allowed simultaneous quantification of several key components (uranium, neptunium, plutonium, nitric acid) in these mixtures in an effective and elegant way. The content of all key components was quantitively determined with mean relative errors not exceeding 10%. It was shown that the employment of the whole spectra or their certain continuous regions for a PLS calibration enables to decrease the analytical errors compared to the use of a single wavelength in an ordinary least squares approach. The results of this research imply that the development of on-line techniques for SNF reprocessing monitoring is fully possible and can be based on optical spectroscopy methods combined with multivariate data processing techniques.