<p>The popularity of new self-healing hydrogels and their application in biomedicine is constantly growing. To ensure self-healing properties, one of the strategies is to add salts of multivalent metals at the stage of gel synthesis, which are capable of participating in ion-coordination interactions and forming sacrificial bonds. However, their influence on the final structure of the hydrogel and the distribution of different types of water in it is not entirely clear. To study the relationship between the structure and water distribution in the gel on its physical properties, acrylic hydrogels were synthesized based on a copolymer of acrylic acid and acrylamide in the presence of various iron salts: FeCl₃, FeC₂O₄ and Fe(NH₄)₂(SO₄)₂. The network parameters were calculated from the sorption properties of the hydrogels. The water composition was studied by DSC, isothermal TGA and time-resolved ATR-FTIR spectroscopy. The mechanical properties were studied using dynamic mechanical analysis to assess the rigidity, stability and strength of the systems. Our results demonstrate a clear correlation between the iron salt type, the hydrogel structure, and its final properties. Unlike the pure AA-<i>co</i>-AAm hydrogel, all tested iron salts reduced the overall crosslinking density, evidenced by increased equilibrium swelling, larger mesh size, and decreased elasticity. However, the degree and mechanism of this effect strongly depend on the oxidation state of the iron ion and its counterion, leading to markedly different mechanical properties and water distribution patterns, from rigid Fe³⁺-crosslinked networks to highly swollen Fe²⁺-containing gels.</p> Graphical abstract <p></p>