In the current study, hybrid electrospun ethylene vinyl alcohol (EVOH) fibers reinforced with bacterial cellulose nanowhiskers (BCNW) were developed and characterized. Additionally, electrospinning was suggested as a method for the incorporation of well-dispersed BCNW into an EVOH matrix by melt compounding. With the aim of maximizing the BCNW's loading in the electrospun fibers, an optimized method was applied for generating fibers from solutions containing up to 40 wt % BCNW. As demonstrated by FTIR spectroscopy, it was possible to incorporate BCNW concentrations up to similar to 24 wt %, although a complete incorporation of the nanofiller into the fibers was only achieved with solutions containing up to 20 wt % of the filler, DSC analyses suggested that the incorporation of the nanofiller reduced the crystallinity of the as-obtained EVOH fibers and produced an increase in the glass transition temperature of these during the second heating run. Thermogravimetric analyses showed that even though EVOH protects the nanowhiskers from thermal degradation, the electrospun hybrid fibers present a relatively lower thermal stability than the pure EVOH fibers. FTIR analyses of the samples subjected to different thermal treatments confirmed that the stiffening effect observed by DSC only occurs after melting of the EVOH phase and is cooperative with a partial acid chemical development in the BCNW, which promotes strong chemical interactions between the polymeric matrix and the nanofiller. Finally, the hybrid electrospun fibers were incorporated into pure EVOH by melt compounding to produce composite films. This methodology showed higher stability and dispersion of the BCNW than direct addition of the freeze-dried nanofiller to EVOH. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012