Different characteristic surface structures such as true and hemi spheres, honeycomb, regularly spaced droplets and fibers are created by electrostatic polysaccharide interaction between chitosan and gellan gum via polyion complex formation. Spherical droplet capsules of varying diameters form in solution. Strong fibers can be spun by gravity and by wet spinning in ethanol. These fibers possess a counter ion pairing structure, and exhibit a 'nervation/veining' pattern.