A method for the one-step synthesis of alkyd resins based on glycerol, phthalic anhydride, and vegetable oils using new sulfonated cation-exchangers and Ti-containing metal-polymer nanocomposites as catalysts has been developed. The film-forming properties, composition, structure and molecular weight characteristics of the synthesized resins have been studied by IR, NMR spectroscopy, and gel chromatography. The possibilities of regulating the molecular-weight distribution of the obtained alkyd resins depending on the nature of the catalyst and the reaction conditions have been revealed.