Electrospun fibers are explored as a new system for controlled drug delivery. Novel techniques capable of obtaining polymer nanofibers have been reported in the literature. They include solution blow spinning (SBS), which is a technique to produce polymer nanofibers in the same range as electrospinning, using pressurized gas instead of high voltage. The present study investigates release characteristics of diclofenac sodium encapsulated at three concentrations (5, 10, and 20% w/v) in poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanofibers made by electrospinning and SBS and determines the drug's effect on fiber morphology and structural properties. PHBV nanofibers were characterized using scanning electronic microscopy, differential scanning calorimetry, and X-ray diffraction, and the release profile was examined via UV-Vis spectrophotometry. Both electrospinning and SBS encapsulated diclofenac sodium in PHBV membranes efficiently and effectively. The profile of the in vitro release of diclofenac sodium was dependent on drug concentration and temperature. The drug reduced crystallinity and increased flexibility.