The present work investigates the validity of electrospun borneol-polyvinylpyrrolidone (PVP) nanocomposites in enhancing drug dissolution rates and improving drug physical stability. Based on hydrogen bonding interactions and via an electrospinning process, borneol and PVP can form stable nanofiber-based composites. FESEM observations demonstrate that composite nanofibers with uniform structure could be generated with a high content of borneol up to 33.3% (w/w). Borneol is well distributed in the PVP matrix molecularly to form the amorphous composites, as verified by DSC and XRD results. The composites can both enhance the dissolution profiles of borneol and increase its physical stability against sublimation for long-time storage by immobilization of borneol molecules with PVP. The incorporation of borneol in the PVP matrix weakens the tensile properties of nanofibers, and the mechanism is discussed. Electrospun nanocomposites can be alternative candidates for developing novel nano-drug delivery systems with high performance.