The rapid emergence of antimicrobial resistance warrants an antibiotic‐free approach to counter the bacterial threat in all possible applications of environmental and biomedical domains. In the context of smart wound dressing, besides imparting anti‐infective characteristics in a nonconventional fashion, it is also essential to imbibe multifunctional attributes like excessive biofluid drainage, easy‐to‐peel, optimal gas permeation, etc., for which appropriate material design is a prime requisite. In this work, poly(ε‐caprolactone) (PCL)− an FDA approved biocompatible polyester− is chosen for imparting antimicrobial properties by surface derivatization with molecularly‐dispersed ionic silver over quaternary ammonium moieties through a facile room temperate and organic solvent‐free approach. To render the other characteristics mentioned above, two different systems comprising PCL with varying porosity, namely, electrospun fibers and polyester‐coated cotton gauze, are developed. The dressing materials are thoroughly characterized and assessed for their structural, surface chemical, morphological, wettability, antibacterial, and peel strength properties as a function of surface derivatization steps. The bactericidal performance of the quaternary ammonium‐functionalized surfaces has enhanced manifold (≈7–10) after derivatizing with ionic silver. The in vivo efficacy study employing the dressing materials reveals ionic silver derivatized electrospun fibers as the most promising candidate, followed by cotton gauze‐coated with 5% PCL.