The optimal conditions for the fibers preparation of cellulose acetate (CA) and poly(vinyl pyrrolidone) (PVP) containing triclosan within the fiber were successfully found; the physicochemical characteristics of these fibrous membranes were corroborated by FTIR spectroscopy, thermal analysis, mechanical tests, SEM , and TEM analysis. The formation of composite fibers of CA and PVP containing triclosan at the core of the fiber was evidenced. A comparative study of the release properties of amoxicillin, epicatechin or triclosan embedded into fibers CA/PVP/CA was performed. As more interactions of the drug with CA or PVP occur, slower release of the drug into the release medium takes place. Regarding the drug delivery system design, it is important to consider the possible molecular interactions between the material components and predict how fast or slow the drug will be delivered into the corresponding medium.