AbstractThis work presents a method for the synthesis of multifunctional hydrogels based on polymer framework obtained by UV-initiated polymerization of the acrylic monomers (acrylamide, acrylonitrile, and sulfo-group-containing monomer (3-sulfopropyl acrylate potassium salt, 2-acrylamido-2-methylpropane sulfonic acid, and sodium styrene sulfonate)) in the presence of N,N′-methylenebisacrylamide as a cross-linking agent. Composite polymer/silica nanogels have been created in situ using a TEOS-based sol–gel system and the above-mentioned polymeric matrices. The synthesized material characteristics such as composition, morphology, and thermal stability were explored with FTIR, SEM, and DCS. In addition, the effect of temperature, inorganic component content, sulfo-group-containing monomer to proton conductivity and water uptake have been explored. The obtained hydrogels possess proton conductivity up to 19 mSm/cm with potential implying for application in electrochemical devices and superabsorbent material. This method is user-friendly and cost-efficient, and proceeds in an aqueous environment under atmospheric conditions without the use of heavy metal catalysts.