The subject of our investigations was the process of obtaining alginate/chitosan polyelectrolyte complex (PEC) fibers. In this study, a novel method named "spray-spinning" was developed for the making of these hybrid fibers. In spray-spinning, a chitosan solution was sprayed into a flowing sodium alginate solution and sheared into streamlines. The elongated streamlines subsequently transformed into alginate/chitosan PEC fibers. Average diameter of the fibers increased with the increasing of chitosan concentration used in spinning. The fibers showed a high water-absorbability of about 45 folds of water to their dry weight and retained their integrity after incubation in Minimum Essential Medium (MEM) for up to 30 days. In vitro co-culture experiments indicated that the fibers could support the three-dimensional growth of HepG2 cells and did not display any cyto-toxicity. Moreover, in vivo implanting experiments indicated that the connective tissue cells infiltrated into the implanted fibrous scaffolds in 3 weeks after surgery. These results demonstrated the potential applications of the as-spun fibers in regenerative medicine and tissue engineering.