Multiwavelength spectrometry and reversed-phase high-performance liquid chromatography have been employed for the study of the effect of reduced glutathione and storage time on the pigments of paprika powders. The evaluation of the data by principal component analysis and cluster analysis proved that the storage time exerts the highest effect of the decomposition rate of pigments. The stability of some pigment fractions was modified in the presence of reduced glutathione. However, the effect was of secondary importance. Multiwavelength spectrometry combined with HPLC can be successfully used for the study of the stability of pigments of paprika powder.