Electrospinning is an interesting technique, which provides a facile and an effective mean in producing nonwoven fibrous materials; however, for producing nanofibers, investigation of the electrospinning conditions is very important. In this study, chitosan, gelatin, and their polyelectrolyte complexes (PECs) were electrospun to prepare nonwoven nanofibrous mats. The concentrations of chitosan and gelatin solutions and electric field (kV/cm) were optimized. The solutions were then blended in different ratios (0-100%) to get electrospun nanofibrous mats. Solution concentration and electric field showed pronounced effect on the electrospinnability and fiber diameter of these systems. Mostly large beads coexisted with the fibers were observed for chitosan at 1 wt% solution concentration, which then showed good electrospinnability at 2 wt% (nanofiber diameter was 145 and 122 nm at 15 and 20 kV/10 cm, respectively), whereas gelatin showed no electrospinnability below 15 wt% solution concentration and a homogenous fibers network at 15 wt% (149 nm at 20 kV/10 cm). The morphology and diameter of chitosan-gelatin PEC nanofibers varied with the chitosan/gelatin ratio. The crystallinity of chitosan was also observed to reduce with electrospinning and addition of gelatin. POLYM. ENG. SCI., 50:1887-1893, 2010. 2010 (C) Society of Plastics Engineers