Developing environmentally friendly and biodegradable corrosion inhibitors is an important research direction due to the toxicity and non-degradability of conventional carbon steel corrosion inhibitors added to circulating cooling water environments. Polysaccharides in EPSs (Exopolysaccharides) can be used as green corrosion inhibitors, but a low inhibition rate limits their practical application. Chemical modification is widely used to modify the functionality of polysaccharides by altering their physicochemical properties and structures, thereby enhancing or supplementing their functional characteristics. In this study, we employed chloroacetic acid as an esterifying agent to chemically modify Dextran and successfully synthesized a modified polysaccharide derivative with a substitution degree of 0.326. This derivative efficiently inhibited the corrosion of carbon steel in circulating cooling water environments. The carboxymethylated dextran (CM-Dextran) formed after synthesis could adsorb onto metal surfaces to form a protective film, thereby inhibiting metal surface dissolution reactions and exhibiting anodic corrosion inhibition properties. The experimental results showed that the corrosion inhibition efficiency of CM-Dextran after modification increased by up to 57.4%, with a maximum inhibition efficiency of 82.52% at a concentration of 4 mg/mL. This study provides new insights and opportunities for the development of environmentally friendly corrosion inhibitors derived from polysaccharides.