Steam-exploded fibers from flax (Linum usitatissimum) are heterogeneously acetylated using acetic anhydride and sulfuric acid as catalyst, with the aim to modify the surface properties without changing fiber structure and morphology. The acetylation reaction follows first-order kinetics up to a reaction time that depends on catalyst concentration (15 h when using 0.4 vol % of H(2)SO(4) or 50 h with 0.1 vol %). The fibers undergo no structural and/or morphological changes under either reaction condition. On the contrary, surface damage and structural modifications appear after longer reaction times, when the reaction kinetics change. The extent of biodegradation of acetylated fibers, evaluated from the weight percent remaining after 13 days of exposure to previously isolated cellulolytic bacteria Cellvibrio sp., decreases with increasing acetylation degree. After biodegradation the fibers show a higher acetyl content than before the experiment, indicating that the bacteria preferentially biodegrade unsubstituted cellulose, though also acetylated chains are cleaved. Biodegradable acetylated cellulose fibers with modified surface chemistry and unchanged structure are obtained for applications as polymer composite reinforcements.