AbstractThe crystallization of polymers with long side chains proceeds in the form of hexagonal crystal lattice, regardless of the configuration of the backbone chain. For these polymers the ordered structure in the crystalline state as well as in the melt is typical. The tendency to form an ordered structure takes place in the solutions of branched polymers. At polymer critical concentration about 0.5 wt % the gelation process occurred.The structure and properties of gels of acrylic polymers (i.e., polycetylacrylate) inn‐aliphatic alcohols (C7H15OH–C12H25OH) and hydrocarbons (C10H22–C16H34) were studied. The x‐ray patterns show that all the gels have the same interplanar spacings at the wide angles which correspond to the hexagonal cell. The phase transitions and thermodynamic parameters of gel‐solution transition were studied by means of x‐ray and differential thermal analysis. The structure of gels in alcohols and hydrocarbons was found to be different. This difference was explained in terms of specific polymer‐solvent interactions.The kinetics of supermolecular structure formation in gels was investigated using small‐angle light scattering (SMAL) method. Rather good correlation between SMAL and electron microscopic data was found.Some conclusions about the character of the supermolecular structure‐forming process were made and the model of gel struc