This study synthesized two eco-friendly inhibitors—a chitosan–copper metal–organic framework (CS@Cu MOF) and chitosan–Schiff base–Cu complex (Schiff–CS@Cu)—for Q345 steel protection in 3.5% NaCl/1M HCl. Electrochemical and weight loss analyses demonstrated exceptional corrosion inhibition: untreated specimens showed a 25.889 g/(m²·h) corrosion rate, while 100 mg/L of CS@Cu MOF and Schiff–CS@Cu reduced rates to 2.50 g/(m²·h) (90.34% efficiency) and 1.67 g/(m²·h) (93.56%), respectively. Schiff–CS@Cu’s superiority stemmed from its pyridine–Cu²⁺ chelation forming a dense coordination barrier that impeded Cl⁻/H⁺ penetration, whereas CS@Cu MOF relied on physical adsorption and micro-galvanic interactions. Surface characterization revealed that Schiff–CS@Cu suppressed pitting nucleation through chemical coordination, contrasting with CS@Cu MOF’s porous film delaying uniform corrosion. Both inhibitors achieved optimal performance at 100 mg/L concentration. This work establishes a molecular design strategy for green inhibitors, combining metal–organic coordination chemistry with biopolymer modification, offering practical solutions for marine infrastructure and acid-processing equipment protection.