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Preparation of biodegradable polymers is an actual task of modern science as such substances possess a wide range of useful properties. Two main fields of their application are tissue engineering and food package.1,2 The most suitable way to synthesize such polymers is the ring-opening polymerization (ROP) of lactones being achieved with metal complexes. Zinc complexes are among the most active ROP initiators and represent good alternative to other existing ones used in preparation of biodegradable polyesters in terms of activity, stereoselectivity and biocompatibility.3,4Having a number of advantages, aluminum or tin-based ROP initiators are often prawn with such drawbacks as toxicity, high temperatures in technological processes (higher than 140oC) or high PDI values of the polymers. Taking all these points into consideration, search for new initiators free from these drawbacks is an actual task. So, the aim of this work is the synthesis and characterization by NMR spectroscopy, elemental analysis and in solid state by X-ray analysis of new zinc ROP initiators based on bulky substituted dialkylentriamine ligands and study of their catalytic activity in the polymerization of ε-caprolactone.