A series of Al catalysts with N,N′-diaryloxalamidate and N,N′-diaryldithiooxalamidate ligands were synthesized, and their εcaprolactone polymerization rates were determined in this study. Of the Al complexes bearing N,N′-diaryldithiooxalamidate, [Ph H NCS] 2 Al 2 Me 4 exhibited the highest catalytic activity (conv. of poly-ε-caprolactone = 94%; [ε-caprolactone]:[[Ph H NCS] 2 Al 2 Me 4 ]:[benzyl alcohol] = 100:0.5:2 with [ε-caprolactone] = 2 M at 25 °C after 20 min), and of the Al complexes bearing N,N′-diaryldioxalamidate, [Ph H NCO] 2 Al 2 Me 4 exhibited the highest catalytic activity (conv. of poly-ε-caprolactone = 94%; [εcaprolactone]:[O H Al 2 Me 4 ]:[benzyl alcohol] = 100:0.5:2 with [ε-caprolactone] = 2 M at 25 °C after 30 min). The Al complexes bearing N,N′diaryldithiooxalamidate demonstrated a greater catalytic activity (1.4−7.3fold) than Al complexes bearing N,N′-diaryldioxalamidate. Density functional theory calculations revealed that [Ph iPr NCS] 2 Al 2 (OMe) 4 with a weaker Al−OMe bond and less repulsion of the highest transition state TS1 revealed the lower potential energy of TS1 compared to [Ph iPr NCO] 2 Al 2 (OMe) 4 and further exhibited a higher polymerization rate than [Ph iPr NCO] 2 Al 2 (OMe) 4 .