One of the most important trends in developments in electrospinning is to combine itself with traditional materials production and transformation methods to take advantage of the unique properties of nanofibers. In this research, the single-fluid blending electrospinning process was combined with the casting film method to fabricate a medicated double-layer hybrid to provide a dual-phase drug controlled release profile, with ibuprofen (IBU) as a common model of a poorly water-soluble drug and ethyl cellulose (EC) and polyvinylpyrrolidone (PVP) K60 as the polymeric excipients. Electrospun medicated IBU-PVP nanofibers (F7), casting IBU-EC films (F8) and the double-layer hybrid films (DHFs, F9) with one layer of electrospun nanofibers containing IBU and PVP and the other layer of casting films containing IBU, EC and PVP, were prepared successfully. The SEM assessments demonstrated that F7 were in linear morphologies without beads or spindles, F8 were solid films, and F9 were composed of one porous fibrous layer and one solid layer. XRD and FTIR results verified that both EC and PVP were compatible with IBU. In vitro dissolution tests indicated that F7 were able to provide a pulsatile IBU release, F8 offered a typical drug sustained release, whereas F9 were able to exhibit a dual-phase controlled release with 40.3 ± 5.1% in the first phase for a pulsatile manner and the residues were released in an extended manner in the second phase. The DHFs from a combination of electrospinning and the casting method pave a new way for developing novel functional materials.