The exclusive introduction of end groups into biobased aliphatic polyesters containing vinyl chain ends, prepared by ADMET polymerization of nonconjugated diene monomers, has been achieved by adopting olefin metathesis with a molybdenum-alkylidene catalyst followed by treatment with various aldehydes, and their quantitative introductions were confirmed by grafting PEG with certified M (n) values. The end-functionalized polyesters demonstrated unique emission and thermal properties through an interaction of the end groups; both melting and crystallization temperatures are affected by the end groups as well as the M (n) values.