A series of four dizinc complexes coordinated by salen or salan ligands, derived from ortho-vanillin and bearing (±)-trans-1,2-diaminocyclohexane (L₁) or 2,2-dimethyl-1,3-propanediamine (L₂) backbones, is reported. The complexes are characterized using a combination of X-ray crystallography, multinuclear NMR, DOSY, and MALDI-TOF spectroscopies, and elemental analysis. The stability of the dinuclear complexes depends on the ligand structure, with the most stable complexes having imine substituents. The complexes are tested as catalysts for the ring-opening copolymerization (ROCOP) of CO₂/cyclohexene oxide (CHO) and phthalic anhydride (PA)/CHO. All complexes are active, and the structure/activity relationships reveal that the complex having both L₂ and imine substituents displays the highest activity. In the ROCOP of CO2/CHO its activity is equivalent to other metal salen catalysts (TOF = 44 h⁻¹ at a catalyst loading of 0.1 mol %, 30 bar of CO₂, and 80 °C), while for the ROCOP of PA/CHO, its activity is slightly higher than other metal salen catalysts (TOF = 198 h⁻¹ at a catalyst loading of 1 mol % and 100 °C). Poly(ester-block-carbonate) polymers are also afforded using the most active catalyst by the one-pot terpolymerization of PA/CHO/CO₂.