Two drawbacks of the traditional electrospinning process when used for producing nanofibers for drug release are that clogging of the spinneret is often experienced, and the fibers produced often exhibit a tailing-off of drug release over sustained periods. The present study investigates the preparation of ferulic acid (FA) sustained-release cellulose acetate (CA) nanofibers, in which a third component, polyvinylpyrrolidone (PVP), was included into the nanocomposites for an improved sustained drug release profile. A modified coaxial electrospinning process, in which only organic solvent N, N-dimethylacetamide was used as a sheath fluid, was exploited for a smooth and continuous fabrication of multiple-component nanofibers. Under an applied voltage of 16 kV and an optimized sheath-to-core flow rate ratio of 0.11, three types of FA/ PVP/CA composite nanofibers (with varied of PVP content) were generated. These nanofibers had higher quality in terms of size and distribution of nanofiber diameter, as indicated by FESEM images. Analysis of double-and triple- component nanofibers by XRD, DSC, and ATR-FTIR confirmed the compatibility of components producing homogenous fibers in both cases, but the triple-component nanofibers exhibited better release profiles over sustained periods than the double-component nanofibers in terms of release completeness, reduced tailing-off, and adjustable release rates. The modified coaxial process and the resulting multiple-component nanocomposites should provide a new way for developing novel drug sustained materials and drug delivery systems.