A series of five-membered ring aluminum complexes bearing thiol-Schiff base ligands were synthesized, and their application in the ring-opening polymerization of ε-caprolactone (CL) was investigated. The complexes exhibited dramatically higher catalytic activity than the six-membered ring S2AlMe2 complex (approximately 4- to 10-fold higher) and the five-membered ring L5-PhAlMe2 complex (approximately 7- to 19-fold higher). Moreover, a shorter induction period was observed when the five-membered ring aluminum complexes bearing thiol-Schiff base ligands were used compared with the other types of aluminum complexes bearing Schiff base ligands. The electron-withdrawing groups enhanced the catalytic activity of the Al complexes compared with the electron donating groups. The thiol-Schiff base ligand and the five-membered ring aluminum catalysis had a synergistic effect that was stronger than the combination of their individual effects.