A novel series of starch esters was prepared, which varied both in degree of substitution (DS) and in ester group chain length (C-2 to C-6). Proton nuclear magnetic resonance-based characterization of esterified starch polymers was determined to be superior to standard saponification digestion (SD) analysis. The effects of starch modification on the anaerobic biodegradation potential for the polymer were assessed using the biochemical methane potential (BMP) protocol. Results indicate that increasing the starch ester group chain length necessitates lower levels of substitution to achieve substantial biologic degradation of the polymer.