Synthesis and characterization of a new family of aluminum, magnesium, and zinc complexes supported by (benz)imidazolin-2-iminato ligands are reported herein. Under different reaction conditions, (benz)imidazolin-2-imine ligands reacted with metal alkyl precursors to afford the corresponding complexes, displaying mononuclear, binuclear, and trinuclear structures. Reaction in 1:1 stoichiometry at room temperature afforded the simple Lewis acid-base adducts, which exhibited distorted tetrahedral geometries around the metal centers, whereas high temperature reactions gave rise to dimeric complexes, with each metal bridging two (benz)imidazolin-2-imine ligands to form a four-membered metallacycle ring at the center of the complexes. The catalytic ring opening polymerization (ROP) of ϵ-caprolactone was studied using these complexes as precatalysts in the presence of isopropanol, and very high activities were observed, affording high/medium molecular weight poly(ϵ-caprolactone) products with low polydispersity indices. Detailed kinetic studies revealed that the polymerizations proceeded in a living manner and molecular weights of the polymers could be precisely controlled.