Different characteristic surface structures such as capsules, regularly spaced droplets and fibers are made by electrostatic interaction between cationic chitosan and anionic poly(alpha,L-glutamic acid) via poly-ion complex formation. Spherical droplet capsules of varying diameters form in solutions. The strong fiber are spinnable by gravity and by a wet spinning in ethanol. The resulting PLG composite fiber is water-insoluble, and has a potential as a new poly(alpha-amino acid) fiber technology.