Based on material published between 1989 and 2018 in this paper high performance liquid chromatography and electromigration techniques used in studies of natural dyes that can be found in historical objects are rewieved. Different aspects of analysis have been discussed: the stationary and mobile phase, the choice of sample solvent, methods of extraction and detection, including sensitivity parameters, such as LOD and/or LOQ. The discussed dyes have been divided into three categories (a) red antraquinone dyes along with dyes extracted from bark and tree juices, (b) yellow flavonoid dyes and saffron and (c) blue indigoid dyes. The main markers (chromophores or auxochromes) typical for each dye source were presented which allows to identify specific species of source plants and animals. The first part of the study involved the analysis of most critical findings when it comes to HPLC or represented an significant analytical approach. The second part of the study is focused on different aspects of electromigration techniques application in analysis of natural dyes with special attention paid on such parameters as the running buffer/mobile phase composition and sample solvent. Detection methods along with LOD and LOQ comparison in HPLC and electromigration techniques were also discussed. Methods of sample preparation, such as hydrolysis and extraction, used in HPLC and electromigration techniques were also briefly discussed.
Keywords: Identification of historical dyes; capillary electrophoresis; high performance liquid chromatography; micellar electrokinetic chromatography; works of art.