In drug delivery systems, it is crucial to develop a drug carrier capable of regulating both the drug-release rate and the drug-release ratio. This study proposes a method for controlling the drug-release ratio/rate using doxorubicin-loaded natural composite films composed of polysaccharides (cellulose, chitin, chitosan, or cellulose nanocrystal) and mineral substances (MMT: montmorillonite). We succeeded in controlling the doxorubicin release ratio from 25 to 88% depending on the natural polysaccharide. Likewise, the reduction rate differed depending on the type of natural polysaccharide, whereas the reduction in release was achieved by mixing MMT. Cellulose had the largest reduction in the drug release ratio, approximately 30%, and cellulose nanocrystals showed little change. Furthermore, we conducted a skin permeation test on the natural polysaccharide film with the highest release rate to confirm its transdermal permeability potential. The polysaccharide doxorubicin-loaded film sustainably released doxorubicin for 2 days, which indicated the potential of a carrier for DDS applications.