Herein we demonstrated a novel lipase-catalyzed synthesis of isotactic D-/L-poly(aspartate-octane-diol) ester containing long chain alcohols backbone and discovered their stereocomplex feature with an increased T-m for the first time. Simple design of monomer structures not only overcomes the inherent selectivity limitation of enzyme used, but also achieves totally isotactic polyester products. By crystallizing the mixed enantiopure isotactic polyesters in different solvents, the formation of amorphous mixture, homocrystallites or stereocomplex crystallites were observed, respectively. This study is expected to open up a new way to prepare various stereocomplex polyesters containing a long-chain aliphatic alcohol backbone and a wide variety of functional groups.