The numerous applications of dextrins resulting from the heating of potato starch with alpha-amino acids prompted me to check the thermal reactions of starch with hydroxy acids and their lactones, such as citric acid, lactic acid, tartaric acid, and coumarine. The course of reactions was observed by means of Simultaneous TG/DSC Thermal Analyser. The thermal reactions were carried out on convectional and microwave heating. The course of reactions under such conditions was compared and properties of resulting dextrins were recognized. The structure and properties of products were obtained from FTIR spectra, water solubility tests, and pH measurements. It was found, that hydroxy acids and/or products of their thermal transformations reacted with starch and/or resulting dextrins producing esters or crosslinking esterification of dextrins took place. The properties of new dextrins were presented in order to check, in further studies, their application for selective flotation of complex metal ores and their suitability as prebiotics.