The kinetics of carbon dioxide and propylene oxide copolymerization was investigated in order to obtain Arrhenius parameters for the reaction in the presence of the efficient binary catalytic system (salen)Co(DNP)/[PPN]Cl. The reaction rate was followed by measuring the uptake of carbon dioxide during copolymerization. The steady-state rate of the reaction reaches a maximum value at carbon dioxide pressure of 0.6–0.7 MPa. At the reaction conditions, the dependences of the reaction rate on the concentrations of reagents follow the first-order kinetic low. The value of effective activation energy is equal to 45.7 ± 2.0 kJ/mol, and pre-exponential factor in the Arrhenius equation is equal to (5.1 ± 0.1) × 105 L2/(mol2 s). The poly(propylene carbonate) produced was shown to be a regio-regular copolymer with a bimodal molecular weight distribution.