The use of a catalyst is required to synthesize poly(D,L-lactide) (PLA) and tin (II) 2-ethylhexanoate could be highlighted among them. However, this kind of catalysts can produce bio-dangerous compounds limiting the PLA in medical applications, therefore there is a need to investigate novel bio-safe catalysts. Taking into account this problem, this communication reports the use of micro- and nano-ZnO particles as catalysts for the microwave-assisted polymerization of D,L-lactide. By microwave heating a high monomer conversion (higher than 95%) was achieved in a relatively short reaction time (3 hours). Morphology/size and concentration of ZnO particles presented a strong effect on the production of PLA, star-like microparticles leaded to conversion ca. 25%, well below to the values achieved with the nanoparticles. Furthermore, the formation of a ZnO-PLA hybrid was evidenced by spectroscopic and thermal characterization techniques. The methodology herein developed represents a new pathway for the green synthesis of PLA.