This study presents a method for incorporating cholecalciferol of a poorly water-soluble vitamin into poly(vinyl pyrrolidone) fibers by electrospinning. The poorly water-soluble vitamin was incorporated into water-soluble polymeric matrix of nanofibers with the rapid evaporation of solvent during the electrospinning process. The scanning electron microscope (SEM) images showed that the diameter of nanofibers is range of 0.2-2.9 μm. The physicochemical properties of the composite nanofibers were characterized by using Fourier-transform infrared (FTIR) spectroscopy and Differential scanning calorimetry (DSC). 82.1 % and 51.9 % of cholecalciferol was released in the first 20 s from the composite nanofibers with a drug-to-PVP ratio of 1:4 and 1:2, respectively. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers