A family of zirconium complexes containing bis-, tri- or tetra-BTP ligands (BTP = benzotriazole phenolate) were synthesized and structurally characterized. Treatment of Zr(O(i)Pr)4((i)PrOH) with 2.0 molar equivalents of 2-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol ((C8)BTP-H) or 2-(2H-benzotriazol-2-yl)-4,6-di-tert-butylphenol ((t-Bu)BTP-H) afforded zirconium alkoxide ([((C8)BTP)2Zr(O(i)Pr)2] (1); [((t-Bu)BTP)2Zr(O(i)Pr)2] (2)) in good yield. Similarly, the bis-adduct Zr amide [((t-Bu)BTP)2Zr(NMe2)2] (3) resulted from amine elimination of Zr(NMe2)4 as the metal precursor and (t-Bu)BTP-H as the pro-ligand under a similar synthetic method with a metal to ligand precursor ratio of 1:2 at 0 °C. The reaction of Zr(NMe2)4 with (C8)BTP-H or (t-Bu)BTP-H (4.0 mol equiv.) gave the tetra-adduct zirconium complex ([((C8)BTP)4Zr] (4); [((t-Bu)BTP)4Zr] (5)) in ≧70% yield. Interestingly, the tri-adduct Zr amide [((t-Bu)BTP)3Zr(NMe2)] (6) could be prepared by treatment of 3 with a stoichiometric amount of (t-Bu)BTP-H. The solid-state structure of 6 reveals a monomeric Zr(IV) amide with three (t-Bu)BTP ligands and one -NMe2 group, and the bonding modes between the BTP moiety and the metal centre adopt both N,O-bidentate and O-monodentate types. Zr complexes 1 and 4 incorporating sterically less bulky (C8)BTP ligands were demonstrated to efficiently catalyse not only copolymerization of epoxide with CO2 but also lactide polymerization. The tetra-BTP Zr catalyst 4 was able to copolymerize cyclohexene oxide and CO2 in a controllable manner, generating the high-molecular-weight copolymer (Mw > 10,000 g mol(-1)) and a high degree of carbonate linkages (>90%). Single-site zirconium alkoxide 1 is the most active catalyst for living lactide polymerization in solution among these complexes, giving poly(lactide)s with the expected molecular weights and narrow molecular weight distributions (PDI ≦ 1.25). This is a successful example of utilizing versatile benzotriazole phenolate Zr(IV) catalysts for either the production of biodegradable poly(lactide) or poly(cyclohexene carbonate-co-cyclohexene oxide).