The exploration of efficient catalysts for the ring-opening polymerization of cyclic esters has significant implications for the synthesis of biocompatible and biodegradable polymers. In this work, the simple catalyst lithium bis(trimethylsilyl)amide (LiHMDS) with high activity was explored in detail for the synthesis of polylactide (PLA). Using LiHMDS as the catalyst, various cyclic esters were polymerized to obtain diverse sustainable polyesters, such as poly(lactide), poly(δ-valerolactone), and poly(caprolactone), with controlled molecular weights and narrow molecular weight distributions. PLA synthesis was accomplished in just a few minutes at room temperature, contributing to the sustainable advancement of this polymer.