Additives that exhibit polyelectrolyte behavior such as N,N-dimethylformamide (DMF) may improve the electrospinning characteristics of viscoelastic polymer solutions. DMF additions to the solution lead to extensive jet splaying, thereby reducing the fiber diameter significantly. Nanofibrous structures with diameters of the order of 150 nm can be produced by the addition of about 10 vol.-% DMF to the solvent (chloroform ), DFM additions also yield a narrow, unimodal distribution of fibers, compared to the bimodal distribution typically detected in electrospun polymers.