Polyion complex (PIC) hydrogels possess excellent strength and toughness due to the dynamic and synergetic energy dissipation mechanism associated with the co-existence of both strong and weak bonds, ionic and hydrogen, in their networks. On the other hand, PIC hydrogels usually exhibit poor wet adhesion properties. Furthermore, the role such dynamic energy dissipation mechanism plays in determining interfacial binding is unknown. To address these challenges, here, we report the fabrication of an adhesive PIC hydrogel, poly(sodium p-styrenesulfonate) (NaSS)/poly(acryloyloxyethyltrimethyl ammonium chloride (DAC)–co-2-vinyl-4,6-diamino-1,3,5-triazine (VDT), i.e. PNaSS/P(DAC-co-VDT), by introducing a multi-hydrogen bonding capacity functional co-monomer, VDT, and solvent-induced gel phase separation into the fabrication process. The resulting hydrogel exhibited as high as 174 kPa adhesion strength, with retained high mechanical properties, typically 1.2 MPa tensile strength, 2.12 MPa Young’s modulus, and 452% strain. The mechanical properties of PNaSS/P(DAC-co-VDT) were tunable by adjusting the content of VDT and of the total monomer concentration in hydrogel precursor solutions (Cm), as well as by taking advantage of the Hofmeister effect. The dynamic modulus spectra of PNaSS/P(DAC-co-VDT) hydrogels at different Cm’s in extended frequency windows with time–temperature superposition method (TTS) were acquired and analyzed to explore the influence of polymer entanglement on the hydrogel network structure. The microscopic structure-macroscopic mechanical property relationship of PNaSS/P(DAC-co-VDT) hydrogels at different Cm’s and immersed in different salt solutions was further studied using the Mooney-Rivlin equation and by fitting the tensile data to Creton’s viscoelastic model. This study may provide new insights into designing and constructing strong and tough PIC hydrogel-based adhesives.