Wound management is a crucial aspect of modern healthcare, necessitating innovative and efficient wound dressings. Hydrogel-based dressings have emerged as promising solutions due to their high-water content, biocompatibility, and ability to maintain a moist wound environment. The integration of nanomaterials further enhances functionality, particularly with silver nanoparticles offering antimicrobial properties. In this context, nanocomposite wound dressings with a hierarchical structure, composed of hydrogel films incorporated with silver clusters, are developed. These nanocomposites consist of poly(hydroxyethyl methacrylate)-co-acrylamide (PHEMA-co-AAm) hydrogel films, which maintain a high level of moisture at the wound site, present high mechanical properties, are nontoxic, and facilitate the exchange of water vapor. Additionally, they incorporate silver clusters (AgC) serving as chromophores that provide protection against microbial infections and exhibit periodic structures to encourage the organization of fibroblasts. The AgC are produced through the photoreduction of Ag⁺ ions, characterized by UV-visible and fluorescence spectroscopy, revealing a maximum absorbance of around 515 nm, allowing the structuring of the AgC@PHEMA-co-AAm material. The composite hydrogels are structured through DLW treatment at a 532 nm wavelength, varying the period and cumulative fluence. The resulting material shows optimal physical properties, promotes fibroblast organization, and presents antibacterial activity against Gram (+) and Gram (−) bacteria, demonstrating the material’s potential as wound dressings.