Quaternized chitosan (QCh) was homogeneously:synthesized by reacting chitosan with 3-chloro-2-hydroxypropyltrimethylarnmonium Chloride (CHPTAC) in alkali/urea aqueous solution for the first time. The structure and solution properties of QCh were characterized by using element analysis, FT-IR, C-13 NMR, SEC-LLS, rheology, viscometer, and-potential measurements. Subsequently, polyelectrolyte complex (PEC) hydrogels were constructed by in situ polymerization of acrylic acid (AA) monomers in the concentrated QCh solution. The structure and mechanical behavior of the prepared hydrogels were systematic studied. Because of the high charge density and solubility of QCh, strong electrostatic interactions were formed in the hydrogels and endowed them tough with self-recovery properties. The mechanical behavior of the hydrogels was accurately tuned from stiff and viscoelastic to soft and elastic by changing the poly(acrylic acid) (PAA) content. The regulation mechanism relied on the remarkable difference in the chain segmental Mobility between QCh and PAA. Moreover, the QCh/PAA PEC hydrogels displayed excellent solvent-induced shape-memory behavior due to the reversible properties of the ionic bonds. In summary, we offered a novel modification method for chitosan and opened up a new avenue to construct chitosan-based hydrogels with outstanding mechanical properties.