•Review of HPLC-PCD applied to food analysis.•Coverage of twenty years of research in the field.•Various classes of compounds/analytes are included.•Legislation issues are also discussed.•Sample preparation for each class of compounds is included. High performance liquid chromatography coupled with post–column derivatization is used for increasing the sensitivity and selectivity of the desirable analytes after the chromatographic separation. The transformation of the analytes can be conducted through the addition of a suitable reagent in the eluted stream or the ultraviolet irradiation of the eluted analytes, forming detectable derivatives for ultraviolet or fluorescence detectors. This review focuses on the developed methods using high performance liquid chromatography coupled with post-column derivatization for the determination of substances in food samples during the last two decades. The significance of the determination of each analyte in foods and the existing guidelines in each case are discussed. Preparation of the samples and the analytical methods are commented. For each analyte, official methods and commercially available systems and reagents are mentioned, as well.