A method of forming a polyethercarbonate polyol enhances incorporation of CO2 into the polyethercarbonate polyol. The method provides a catalyst including a multimetal cyanide compound. An H-functional initiator, an alkylene oxide, and CO2 are reacted in the presence of the multimetal cyanide compound in a reactor. The method further provides a CO2-philic compound or a CO2-philic substituent. The CO2-philic compound and substituent enhance incorporation of the CO2 into the polyethercarbonate polyol and reduce formation of cyclic alkylene carbonates, such as cyclic propylene carbonate, which are undesirable byproducts.