PECs of chitosan/κ-carrageenan are prepared in three different volumetric rations. The complex formation is characterized in order to evaluate the blending formation. Blood compatibility is evaluated by protein adsorption (BSA and fibrinogen) and PEC toxicities are determined with fibroblast cell viability and proliferation. The swelling degree of PECs decreases when the amount of chitosan increases. Due to the linked film formation, PECs decrease BSA adsorption and increase fibrinogen adsorption when compared to the pristine chitosan and κ-carrageenan films. Although pristine chitosan and κ-carrageenan films produced similar cell expansion and viability, the PEC 50:50 vol% chitosan/κ-carrageenan PEC may be acceptable as a new scaffold for cell therapies, due to their effect on cell survival.