The ternary copolymerization of vinyl acetate (VA), maleic anhydride (MA) and acrylic acid (AA) or methylacrylate (MAc as a model comonomer), considered as donor-acceptor-acceptor systems, was carried out in p-dioxane in the presence of benzoyl peroxide (BPO) as initiator in nitrogen atmosphere at 70ºC. Constants of copolymerization and complex formation for the monomer systems studied were determined by the Kelen-Tüdös, UV(H-complex) and 1H-NMR (CTC, charge transfer complex) methods, respectively. Analogous H-complex effect is evidenced from comparison of copolymerization of both MA-AA (H-complex) and MA-MAc binary systems in which are realized alternating and random copolymerization, respectively. Hydrolyzed VA- MA-AA terpolymers with different composition containing regular H-complexed fragments in side-chain of macromolecules are displayed different thermal properties, including glass-transition and melting (crystalline phase) behaviors, depending on content of H-bonding fragment. Structural peculiarities (FTIR analysis) and structure-thermal properties (DSC and TGA analyses) and crystalline (X-ray diffraction analysis) relationship of terpolymers synthesized are also discussed.