At the beginning of this study, we aimed to prove that a spatioselective surface modification by esterification would allow for alteration of material properties but still allow for biodegradability. As such, this could be used to inform current legislation and future analytical development to avoid environmental hazards. It seems that by fine control over reaction conditions, it is possible to restrict acetylation to fibril surfaces and that this has a significant impact on the enzymatic digestibility. Even by acetylation on fibril surfaces to a bulk DS of 0.02, where only 6-OHs are acetylated, results in a change in the CtA. No major changes in mechanical properties (dry or wet) are apparent. Since there is not a significant change in CtA at these very low bulk DS values, the changes in enzymatic digestibility are also possibly related to enzyme selectivity for surface acetylated chains or changes in swelling of the sample in aqueous environments, as shown through SAXS analysis.