Traditional synthesis methods for polyzwitterionic hydrogels involve harsh conditions, such as thermal or UV irradiation, prolonged durations, and high monomer concentrations. Herein, we address these challenges at the meantime by proposing a novel chemical method, called hydration‐shielding accelerated self‐catalytic polymerization (HS‐A‐RP), facilitating the preparation of polyzwitterionic hydrogels. The discovery is that polyvinyl alcohol (PVA) chains can generate hydration shielding around hydrated zwitterionic monomers, promoting their effective aggregation and rapid crosslinking polymerization under the assistance of silver ions (Ag+)‐potassium persulfate (S2O82‐) redox catalyst. The HS‐A‐RP method performs under mild condition (‐5℃ to 37℃) without extra energy, overcomes the critical monomer polymerization concentration limitation (wt%: 0.3%), and completes within an ultra‐short polymerization time (<60 s). The prepared polyzwitterionic hydrogels possesses a denser network and superior mechanical properties compared to those prepared by traditional thermal/UV methods, exhibiting good anti‐swelling behavior, excellent lubrication performance, and significant antibacterial and anti‐fouling properties. These significant advances endow HS‐A‐RP with attractive application potentials in manufacturing functional hydrogel coatings for biomedical device, in situ encapsulation of thermally sensitive materials, and excellent sand fixation abilities. Moreover, HS‐A‐RP method is suitable for scalable manufacture and decorative coating of polyzwitterionic hydrogels on diverse substrates in extreme environmental conditions.
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