Marine biofouling is formed by the adhesion of organic matter, bacteria, a variety of micro-animals, and micro-plants on the surface of marine materials, which has caused serious harm to marine activities and resources development. In this paper, polysaccharide polyelectrolyte complex (PEC) hydrogel films were prepared with oppositely charged chitosan quaternary ammonium salt (HACC) and sodium alginate (SA) by assembly. Due to the synergistic effect of hydrogen bonds, electrostatic interaction, and metal coordination bonds, the hydrogel film has excellent mechanical properties (fracture strength of 8.65 MPa). In addition, a Fe-TCPP@HACC/SA PEC hydrogel film was prepared by the further introduction of 4-carboxyphenyl porphyrin iron metal cluster (Fe-TCPP) composite PEC, which endowed the hydrogel film with the expected excellent antibacterial properties (the diameter of the inhibition zone is 2.5 mm), protein adsorption resistance (protein adsorption amount of 28.52 mg/g), and diatom adhesion resistance (diatom adhesion ratio of 9.17%).Therefore, this novel hydrogel film has potential applications in the field of marine biological pollution antifouling.