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This research investigated a novel process to prepare polyester from corn stover through liquefaction and cross-linking processes. First, corn stover was liquefied in organic solvents such as ethylene carbonate and ethylene glycol with catalysts (sulfuric acid) at moderate temperature under atmospheric pressure. The liquefied corn stover was rich in polyols, which can be directly used as feedstock for making polymers without further separation or purification. Secondly, polyester was made from the liquefied stover by cross-linking with multi-functional carboxylic acids and/or cyclic acid anhydrides. The strength of polyester is fair and acceptable. The polyester is stable in cold water and organic solvents but readily biodegradable indicated by 82% weight loss when buried in damp soil for ten months.