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The representative of the new family of mechanically reversible gels is described. The gel is formed by mixing of an aqueous solution of non‐stoichiometric interpolyelectrolyte complex of poly (sodium methacrylate) and poly(N‐ethyl‐4‐vinylpyridinium bromide) containing a certain amount of covalent links between oppositely charged polyions, with aqueous solution of poly(potassium vinylsulfate). The gelation mechanism arises to the partial replacement of the electrostatic contacts between the polycation and poly(methacrylate) anion in the original polycomplex with those between the polycation and poly(vinylsulfate) polyanion. The network of the gel is most probably formed by the nodes consisting of covalent links and interpolyelectrolyte double‐strand electrostatic clusters, united by poly(sodium methacrylate) tie‐chains.

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