Five novel magnesium alkoxides supported by drug chelating agents pridinolumwere successfully synthesized and characterized. Direct reaction of PriOH and VenlOH with MgBu 2 (1:1) in toluene gives the dimeric compounds [Mg(μ,η 2 -OPri) n Bu] 2 (1) and [Mg(μ,η 2 -VenlO) n Bu] 2 (2), respectively. Furthermore, the crystallization of an equimolar mixture of 1 and 2 in toluene yields heteroleptic magnesium complex [Mg(μ,η 2 -OVenl)(η 1 -OPri)] 2 (3). Moreover, reactions of 1 and 2 with 2 molar equivs of the corresponding drug−ligands give the homoleptic magnesium bis-alkoxides [Mg(μ,η 2 -OPri)(η 1 -OPri)] 2 (4) and [Mg(μ,η 2 -OVenl)(η 1 -OVenl)] 2 (5). The treatment of compound 1 with 2 equivs of VenlOH or 2 with 2 equivs of PriOH leads to the formation of 3. Complexes 1−5 were characterized by elemental analysis, nuclear magnetic resonance, and single crystal Xray diffraction (for 1−4). It was found that complexes 1−5 are efficient initiators of the ring-opening polymerization of L-LA, yielding PLA-OPri and PLA-OVenl conjugates, respectively. Moreover, the ring-opening polymerization of L-LA initiated by 3 led to the simultaneous generation of a blend of poly-L-lactide conjugates with end-capped VenlO and PriO groups.