Riboflavin (RF) is a light sensitive compound and is known to form a number of photoproducts. These photoproducts possess the same nucleus and may interfere in the analysis of RF by UV and visible spectrometry. Therefore, it is necessary to apply the methods of multicomponent spectrometric analysis to quantify the vitamin and its photoproducts accurately. Such methods are useful in the study of the kinetics of photodegradation reactions of RF to obtain accurate and reliable results. Any interference in these methods due to linear or nonlinear irrelevant absorption of the minor unknown products can be accounted for by the application of appropriate correction procedures prior to kinetic treatment. Various factors affecting the accuracy, precision and selectivity of these analytical procedures are also discussed. This review highlights the principles and applications of multicomponent spectrometric methods and their application to the simultaneous determination of RF and its major photoproducts in degraded solutions to evaluate the kinetics of degradation.