A novel β‐ketimine ligand supported titanium complex, [Ti (DippNHC(Me)=CHC(Me)O2)Cl2] (2) enabling competent ring‐opening polymerization (ROP) of cyclohexene oxide (CHO) and copolymerization (ROCOP) of CHO and glutaric anhydride (GA) is unveiled. Incredibly well‐controlled poly(cyclohexene oxide) (PCHO) with a range of molecular weights and narrow polydispersity index (PDI) is achieved. The ROP reaction proceeded under mild reaction conditions without the aid of any exogenous initiator. The thermal properties of the polyethers showed a glass transition temperature (Tg) ranging from 60‐69˚C in the DSC curve and high thermal stability of the polymers up to 387˚C in the TGA curve. The Ti(IV) catalyst additionally showed superior activity in the ROCOP of CHO and GA. ROCOP reactions were performed using a diverse range of CHO and GA monomer equivalents, demonstrating the random insertion of epoxide units per glutaric anhydride and forming a random copolymer.