Abstract <p>This paper discusses the effect of the structure of butadiene–methylstyrene thermoplastic elastomers on the adhesive properties of adhesives based on them. The physicomechanical characteristics of films cast from a solution in methylene chloride have been determined. The molecular-weight characteristics of thermoplastic elastomers have been determined using gel permeation chromatography, and the microstructure has been determined using IR Fourier spectroscopy. Thermogravimetric analysis and differential scanning calorimetry have been used to study temperature and energy characteristics of thermoplastic elastomers, which indicate that the butadiene–methyl styrene thermoplastic elastomer sample has a more mobile butadiene block, which is responsible for the adhesion of the material, than the butadiene–styrene sample does.</p>