A simple method to obtain novel nanofibers composed of polyelectrolyte complexes (PECs) has been proposed. It consists of the electrospinning of a mixed homogeneous solution of polyelectrolyte partners, and the formation of PEC during the electrospinning. This was achieved by careful choice of the composition of the spinning solutions. Chitosan was the polycationic partner, with either a weak polyacid [poly(acrylic acid), PAA] as a counterpart or a strong one [poly(2-acrylamido-2-methylpropanesulfonic acid), PAMPS]. The fibrous mats were composed of nanofibers with mean diameters of ca. 100 nm. They retained their integrity over the pH range which is typical of the corresponding PEC.