In this work, a photo-polymerization route was used to obtain potassium acrylate-co-acrylamide hydrogels with enhanced mechanical properties, well-defined microstructures in the dry state, and unique meso- and macrostructures in the hydrated state. The properties of the hydrogels depended on the concentration of the crosslinking agent. Mechanical properties, swelling capacity, and morphology were analyzed, showing a well-defined transition at a critical concentration of the crosslinker. In terms of morphology, shape-evolving surface patterns appeared at different scales during swelling. These surface structures had a noticeable influence on the mechanical properties. Hydrogels with structures exhibited better mechanical properties compared to unstructured hydrogels. The critical crosslinking concentration reported in this work (using glycerol diacrylate) is a reference point for the future preparation of multistructured acrylic hydrogel with enhanced properties.