A fibrous scaffold comprising of chitosan (CS) and poly(E-caprolactone) (PCL) was electrospun from a novel solvent mixture consisting of formic acid and acetone. CS concentration was varied from 0.5% to 2% by fixing PCL concentration as a constant (6%). Selected CS concentration (1%) was further blended with 4-10% PCL to obtain fine nanofibers. The composition of mixing was selected as 25:75 (1:3), 50:50 (1:1) and 75:25 (3:1) of CS and PCL Lower concentrations of PCL resulted in beaded fibers where as 8% and 10% of PCL in lower compositions of chitosan resulted in fine nanofibers. Viscosity and conductivity measurements revealed the optimum values for the spinnability of the polymer solutions. Optimized combination of CS and PCL (1% CS and 8% PCL) in 1:3 compositions was further characterized using SEM, FTIR, AFM and TG-DTA. The developed electrospun CS/PCL scaffold would be an excellent matrix for biomedical applications. (c) 2009 Elsevier Ltd. All rights reserved.