The constant increase in the demand for safe and high-quality food has generated the need to develop efficient methods to evaluate food composition, vitamin C being one of the main quality indicators. However, its heterogeneity and susceptibility to degradation makes the analysis of vitamin C difficult by conventional techniques, but as a result of technological advances, vibrational spectroscopy techniques have been developed that are more efficient, economical, fast, and non-destructive. This review focuses on main findings on the evaluation of vitamin C in foods by using vibrational spectroscopic techniques. First, the fundamentals of ultraviolet–visible, infrared and Raman spectroscopy are detailed. Also, chemometric methods, whose use is essential for a correct processing and evaluation of the spectral information, are described. The use and importance of vibrational spectroscopy in the evaluation of vitamin C through qualitative characterization and quantitative analysis is reported. Finally, some limitations of the techniques and potential solutions are described, as well as future trends related to the utilization of vibrational spectroscopic techniques.