This paper introduces a new delivery system for rapid and controlled drug release. Mixture of hydrophilic, (poly vinyl alcohol, PVA, and randomly methylated β-cyclodextrin, RM β-CD), and hydrophobic (poly D , L -lactide, PLA, and poly D , L -lactide-co-glycoside, PLGA) polymers were electrospun to make a multi-layered/multicomponent nanofiber mat. The release characteristics of the drug were modified using the layer by layer approach to help compensate the limitation of the individual materials. Incorporation of RM β-CD to the PVA solution was able to significantly decrease the degradation rate of the resulting fiber mat from a few weeks to a few seconds. Hydrophilic polymer mat (PVA-RM β-CD) can dissolve in the release media instantly and provide rapid release of the drug. This characteristic makes such carriers suitable as sublingual delivery systems in the treatment of acute disorders. Polyesters, PLA and PLGA, can control drug release via hydrolysis of the polymer and provide sustained and controlled release of the drug. Blends of these hydrophilic and hydrophobic polymers can effectively prolong drug release and decrease physiological toxicity resulting from fast release of drugs. These carriers may be suitable for the treatment of chronic disease where sustained release of the drug is required.