Electrospun polymer nanofibers, due to their high surface area‐to‐volume ratio, high porosity, good mechanical strength, and ease of functionalization, appear to be promising multifunctional materials for biomedical applications. Thanks to their unidirectional structure, imitating the extracellular matrix (ECM), it they can be used as scaffolds for cell adhesion and proliferation. Additionally, the incorporation of active groups inside nanofiber can give properties for bactericides. The proposed nanomats incorporate nanoparticles templated within the electrospun nanofibers that prevent infections and stimulate tissue regeneration. The generated hybrid electrospun nanofibers are composed of a copolymer of L‐lactide‐block‐ε‐caprolactone (PL‐b‐CL), 70:30) blended with homopolymer polyvinylpyrrolidone (PVP) and gold (Au) nanoparticles. A low cytotoxicity and slightly increased immunoreactivity stimulated by the nanomat were observed. Moreover, the decoration of the hybrid nanomat with dendronized silver nanoparticles (Dend‐Ag) improved their antibacterial activity against antibiotic‐resistant P. aeruginosa. The use of Dend‐Ag for decorating offers several functional effects. Namely, it enhanced the antibacterial properties of the produced nanomats and induced a significant increase within macrophages’ cytotoxicity. The unidirectional nanostructures of the generated hybrid nanomats demonstrated unique collective physiochemical and biological properties suitable for a wide range of biomedical applications. Here, the antibacterial properties facilitate an optimal environment, which can contribute to accelerated wound healing.This article is protected by copyright. All rights reserved