•Novel ω-hydroxy-substituted cellulose esters synthesized by hydroboration–oxidation.•Standard hydroboration conditions gave undesired ester saponification or reduction.•9-BBN hydroboration reagent and NaOAc oxidation catalyst successfully suppressed ester loss.•Hydroboration–oxidation compliments olefin cross-metathesis, transforms ω-unsaturated- to novel ω-hydroxy-cellulose esters. We describe the first synthesis of hydroxy-functionalized polysaccharide esters via chemoselective olefin hydroboration–oxidation in the presence of ester groups. Cellulose esters with terminally olefinic side chains were first synthesized by esterification of commercially available cellulose esters (e.g., cellulose acetate) with undec-10-enoyl chloride or pent-4-enoyl chloride. Subsequent two-step, one-pot hydroboration–oxidation reactions of the cellulose esters were performed, using 9-borabicyclo3.3.1nonane as hydroboration agent, followed by oxidizing the intermediate borane to a hydroxyl group using mildly alkaline H2O2. Sodium acetate was used as a weak base to catalyze the oxidation, thereby minimizing undesired ester hydrolysis. Characterization methods including FTIR, 1H, and 13C NMR proved the selectivity of the hydroboration–oxidation pathway, providing a family of novel cellulose ω-hydroxyalkanoyl esters that were previously difficult to access.