In this study, a series of Al complexes bearing amidates, thioamidates, ureidates, and thioureidates were synthesized and their catalytic activity for ε-caprolactone (CL) polymerization was evaluated. SPr-Al exhibited a higher catalytic activity than OPr-Al (3.2 times as high for CL polymerization; [CL] : [SPr-Al] : [BnOH] = 100 : 0.5 : 2; [SPr-Al] = 10 mM, conv. = 93% after 14 min at 25 °C), and USCl-Al exhibited a higher catalytic activity than UCl-Al (4.6 times as high for CL polymerization; [CL] : [USCl-Al] : [BnOH] = 100 : 0.5 : 2; [USCl-Al] = 10 mM, conv. = 90% after 15 min at 25 °C). Regardless of whether aluminum amidates or ureidates were present, thioligands improved the polymerization rate of aluminum catalysts. Density functional theory calculations revealed that the eight-membered ring [SPr-AlOMe2]2 decomposed into the four-membered ring SPr-AlOMe2. However, [OPr-AlOMe2]2 did not decompose because of its strong bridging Al-O bond. The overall activation energy required for CL polymerization was lower when using [SPr-AlOMe2]2 (18.1 kcal mol-1) as a catalyst than when using [OPr-AlOMe2]2 (23.9 kcal mol-1). This is because the TS2a transition state of SPr-AlOMe2 had a more open coordination geometry with a small N-Al-S angle (72.91°) than did TS3c of [OPr-AlOMe2]2, the crowded highest-energy transition state of [OPr-AlOMe2]2 with a larger N-Al-O angle (99.63°).