A detailed account of the construction, properties, and practical applications of electrospinning for the fabrication of high-quality ultrafine fibers, suitable for drug delivery, is given. With respect to the electrospinning method, various parameters are of crucial importance. The electrospinning parameters are classified as solution properties, process parameters, and environmental conditions. The solution properties include the polymer concentration, molecular weight and viscosity, the solution conductivity and relative volatility, volatility of the solvent, surface tension, and dielectric constant. The process parameters refer to the flow rate, the applied voltage, the needle diameter, and the distance between the tip of the needle and collector and the geometry of the collector. The environmental conditions include the relative humidity and temperature. All these factors are responsible for a flawless electrospinning process, which leads to the formation of the desirable electrospun nanofibers with the requisite characteristics. In this chapter, it has been shown that the electrospinning technology could provide a useful method for modifying drug release behavior and opens new routes for the development of effective and tailormade drug release carriers.