Construction of robust, stereocomplexed (sc) crystalline material, based on ar ecently discovered infinitely recyclable polymer system, requires blending of enantiomeric polymer chains produced from respective enantiopure,f used six-five bicyclic lactones.H erein, the stereoselective polymerization of the racemic monomer by yttrium catalysts bearing tetradentate ligands is reported, where the tethered donor sidearm switches the heteroselectivity of the catalyst to isoselectivity when it is changed from the b-OMe to b-NMe 2 sidearm. The latter catalyst produces an isotactic stereoblock polymer (P m up to 0.95) that forms the crystalline sc-material with aT m of up to 171 8 8C. This sc-material can be fully depolymerized backt or ac-monomer in aq uantitative yield and purity,thus establishing its circular life cycle. Scheme 1. Stereoselective ROP of rac-CBLt oisotactic or heterotactic PCBL with full recyclability.