Layer-by-layer (LBL) deposition of polyethylenimine-beta-cyclodextrin (PEI-beta-CD) and ferrocene-modified chitosan (Fc-CHT) via host-guest interaction chemistry was developed for the fabrication of low-fouling, antimicrobial, and biocorrosion inhibition multilayer coatings on stainless steel. An electrochemical method is proposed to monitor and determine the LBL deposition process. The resulting multilayer coatings exhibit good resistance to bacterial adhesion, including Pseudomonas sp. and Staphylococcus aureus, and microalgal attachment of Amphora coffeaeformis. Settlement of barnacle cyprids is also significantly reduced on the bilayer-coated substrates. As the number of assembled host guest bilayers increases, the antifouling efficacy, antimicrobial efficiency, and antibiocorrosion performance also improve progressively. The stability and durability of the multilayer coatings were ascertained after a 30-day immersion treatment in seawater. Thus, the multilayer coatings deposited via LBL method are potentially useful as environmentally friendly coatings for combatting biofouling and biocorrosion in marine and aquatic environments.