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Poly(phenylene methylene) (PPM) is a thermally stable, hydrophobic, fluorescent hydrocarbon polymer. Recently, blended PPM has been proposed as a valuable anti-corrosion coating material, and, in particular, rheological additives such as external plasticizers resulted crucial to prevent crack formation. Accordingly, to avoid common problems related to the use of external plasticizers, the development of PPM-related copolymer-based coatings containing n-octyloxy side chains and their anti-corrosion behavior were explored in this study. The aluminum alloy AA2024, widely employed for corrosion studies, was selected as a substrate, covered with a thin layer of a polybenzylsiloxane in order to improve adhesion between the underlying hydrophilic substrate and the top hydrophobic coating. Gratifyingly, coatings with those copolymers were free of bubbles and cracks. The n-octyloxy side-chains may be regarded to adopt the role of a bound plasticizer, as the glass transition temperature of the copolymers decreases with increasing content of alkoxy side-chains. Electrochemical corrosion tests on PPM-substituted coatings exhibited good corrosion protection of the metal surface towards a naturally aerated near-neutrally 3.5% wt.% NaCl neutral solution, providing comparable results to blended PPM formulations, previously reported. Hence, the application of rheological additives can be avoided by use of proper design copolymers.