Organocatalysts are increasingly applied in polymerizations owing to their environmental friendliness, low toxicity, and inexpensiveness, resulting in desirable metal-free polymers. Based on the cooperative dual activation of monomers and chain ends, mono-or bicomponent bifunctional catalytic systems consisting of electrophilic and nucleophilic moieties have been extensively demonstrated for ROP and ROCOP. In particular, thiourea and boron groups demonstrate exceptional activation of lactones and epoxides, respectively, disclosed by Hedrick, Waymouth, Gnanou, Feng, our group, and others. To develop versatile catalysts for switchable ROP and ROCOP, we sought to integrate two electrophilic sites (thiourea and boron) and one nucleophilic site (tertiary amine) in one molecule, based on the intramolecular synergy and the hypothesized specific monomer/chain-end activation: boron activates epoxides via B-O bonds, thiourea and amine activate lactones and chain ends via hydrogen bonds, respectively (Fig. ).