Novel hybrid fibrous membranes with potential application on the biomedical field were successfully developed via electrospinning of blend solutions of two biocompatible and biodegradable polymers, poly (3-hydroxybutyrate-co-hydroxyvalerate) [PHBV] and chitosan. The effect of solvent, using different proportions of trifluoracetic acid (TFA) and 1,1,1,3,3,3-hexafluoro-2-isopropanol (HFIP), PHBV/chitosan ratio, and chitosan molecular weight on solution spinnability, fiber morphology and size, and in vitro degradation were investigated. Continuous nanofiber structures were obtained from pristine PHBV to a PHBV/chitosan ratio of 2:3 (w/w), at 10% (w/v) total polymer concentration. In general, main fiber average diameters increased as chitosan content and molecular weight increased and decreased with the decrease of HFIP content in the solvent. In vitro dissolution tests revealed that the hybrid fibers show much higher degradation rates than the neat PHBV. (C) 2011 Elsevier B.V. All rights reserved.