This work aimed to obtain and characterize chitosan-gum arabic polyelectrolyte complex films loaded with nystatin employing the “Solvent-Casting” technique. These films were covered with electrospun nanofibers of polycaprolactone-polycarbophil (Noveon® AA-1) to improve the mucoadhesivity of the system with the objective of increasing the residence time in the oral zone and act as sustained release systems of the drug. The topography of the films was determined by SEM, while the interaction of the polymers was evaluated by FTIR, DSC and TGA. The antimicrobial activity of the film was tested against a strain of Candida species, and the mucoadhesión capacity was determined in an in vitro model. The films are mucoadhesive and generate sustained release that can be explained by the Korsemeyer-Peppas model. Furthermore, significant antimicrobial activity was found. The films and their components showed a non-toxic to slight cytotoxic activity. These results indicate that these films based on polyelectrolyte complexes, potentiated by electrospun fibers are a plausible system for the controlled release of nystatin in the oral cavity.