Copolymerization of cyclohexene oxide (CHO) with alicyclic anhydrides applying chromium tetraphenylprophyrinato (TPPCrCl, 1) and salophen (SalophenCrCl, 2) catalysts resulted in polyesters or poly(ester-co-ether)s, depending on the nature of the catalyst, presence of a cocatalyst, solvent and type of anhydride. The combination of 1 as catalyst and 4-N,N-dimethylamino-pyridine (DMAP) as cocatalyst in the copolymerization of CHO with succinic anhydride (SA), cyclopropane-1,2-dicarboxylic acid anhydride (CPrA), cyclopentane-1,2-dicarboxylic acid anhydride (CPA) or phthalic anhydride (PA) invariably resulted in a completely alternating topology and therefore a pure polyester. Contrarily, 2 in combination with DMAP did not afford pure polyesters for the copolymerization of CHO with SA or CPrA but did render the alternating topology when CPA or PA was used as anhydride comonomer. Water proved to be an efficient bifunctional CTA affording a,¿-hydroxyl-terminated polyesters without loss of catalytic activity. When CO2 was introduced as additional monomer to CHO and the anhydrides, both 1 and 2 in combination with DMAP as cocatalyst afforded perfect poly(ester-co-carbonate)s. The presence of CO2 effectively prevents the undesirable side reaction of oxirane homopolymerization.