A series of polyion complex (PIC) composite membranes composed of sodium alginate (SA) polyanion and chitosan polycation were prepared by varying the ratio of concentration. The interaction between SA and chitosan was investigated by FTIR, SEM, and X-ray analysis and was related to mechanical properties and the swelling phenomenon. The overall PIC composite membranes showed the following results: the total thickness of the coating layer was thicker than that of pure SA composite, and increased with increasing the concentration of chitosan solution during PIC formation. This result was attributed to the diffusion of chitosan molecules from the liquid solution into the SA matrix, and the incorporation with SA molecules. For the PIC membranes prepared with different concentrations of polymer solution, their structural differences could not be detected from IR spectra but their morphological differences could be noticeably found from SEM. Furthermore, the amorphousness of PIC membranes and their elongation properties at break increased significantly as a function of polymer contents, whereas the tensile modulus decreased because of the physical transition effect.