Reaction of [Zn(μ‐TAG){N(SiMe3)2}]2 {TAG = N=C[N(CH2CH3)2N(CH3)2] (DEDMG), N=C{[NCH2CH2CH2CdH2(N–Cd)]N(CH2CH3)2} (DEPYRG) and N=C{[NCH2CH2CH2CH2CeH2(N–Ce)]N(CH2CH3)2} (DEPIPG)} with 2 equiv. of ethanol (EtOH) and 2 equiv. of HOAr {OAr = OC6H3(CMe3)‐2‐(CH3)‐6 (BMP) or OC6H2[C(CH3)3]2‐2,6‐(CH3)‐4 (4MeDBP)} results in dizinc alkoxides with the general formula [Zn(μ‐OEt)(OAr)(H‐TAG)]2 (1–3). Et2Zn was additionally treated with 2 equiv. of 1,1,3,3‐tetramethylguanidine (H‐TMG) and H‐BMP or HOC6H3(C6H5)2‐2,6 to yield [Zn(BMP)2(H‐TMG)2] (4) and [Zn{OC6H3(C6H5)2‐2,6}2(H‐TMG)2] (5). Complexes 1, 2, 4, and 5 were characterized by single‐crystal X‐ray diffraction. Polymerization of rac‐lactide with 1–5 and [Zn(μ‐OMe)(4MeDBP)(H‐TMG)]2 (6) were found to generate polylactide (PLA). The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FTIR spectroscopy, and 1H and 13C NMR spectroscopic studies.