A straightforward method for immobilizing in situ generated silver nanoparticles on the surface of a photoactivable isosorbide-derived monomer is developed with the objective to design a functional material having antibacterial properties. The photoinduced thiol–ene mechanism involved in these syntheses is described by the electron spin resonance/spin trapping technique. The resulting materials with or without silver nanoparticles (Ag NPs) were used as films or as coatings on glass substrate. The surface of the synthesized materials was characterized by X-ray photoelectron spectroscopy and scanning electron microscopy, and their thermal and mechanical properties were evaluated by dynamic-mechanical thermal tests, differential scanning calorimetry, thermogravimetric analyses, along with pencil hardness, nanoindentation, and scratch resistance tests. The photoinduced formation of Ag NPs is also confirmed by UV spectrophotometry. Finally, a primary investigation demonstrates the antibacterial properties of the isosorbide-derived material against Staphylococcus aureus and Escherichia coli, as well as its cytocompatibility toward NIH 3T3 fibroblastic cells.