Spectral ellipsometry measurement systems are provided including a polarizer that rotates at a first angle and adjusts a polarizing direction of incident light of a measurement sample; a compensator that rotates at a second angle, different from the first angle, and adjusts a phase difference of the incident light; an analyzer that rotates at a third angle and adjusts a polarizing direction of light reflected on the measurement sample; a detector that detects a spectral image from the reflected light; a controller that controls one of the polarizer, the compensator, and the analyzer according to polarizer-compensator-analyzer (PCA) angle sets including the first to third angles; and a processor that receives, from the detector, a first spectral image corresponding to a first PCA angle set and a first wavelength and a second spectral image corresponding to a second PCA angle set and a second wavelength, different from the first wavelength, and generates a polarizer-compensator-analyzer rotating (PCAR) spectral matrix using the first and second spectral images.