A switchable, solvent-free catalytic system was developed in which Al methyl aminebis(phenolate) catalysts selectively initiate the formation of a polyether from cyclohexene oxide under CO2 atmosphere or the ring opening copolymerisation (ROCoP) of cyclohexene oxide and CO2 through the addition of a PPNCl (bis(triphenylphosphine)iminium chloride) cocatalyst to form poly(cyclohexene carbonate).