Reaction of AlMe 3 with S(SiMe 3 )(C 6 H 3 -2-CH 2 NRR′-5-t Bu) (RR′ = C 5 H 10 (1a), C 4 H 8 (1b), Me 2 (1c)), at ambient temperature, affords the amino adducts [AlMe 3 {S(SiMe 3 )(C 6 H 3 -2-CH 2 NRR′-5-t Bu)}-κN] (RR′ = C 5 H 10 (2a), C 4 H 8 (2b), Me 2 (2c)), which undergo TMS elimination upon heating to give the monomeric aminoarenethiolate aluminum complexes [AlMe 2 {S(C 6 H 3 -2-CH 2 NRR′-5-t Bu)-κ 2 S,N}] (RR′ = C 5 H 10 (3a), C 4 H 8 (3b), Me 2 (3c)). Following the same procedure, treatment of AlCl 2 Me and AlCl 3 with 1 yields analogous aminoarenethiolate aluminum complexes with different degrees of methylation, the chloro methyl and dichloro complexes [AlClMe{S(C 6 H 3 -2-CH 2 NRR′-5-t Bu)-κ 2 S,N}] (RR′ = C 5 H 10 (4a), C 4 H 8 (4b), Me 2 (4c)) and [AlCl 2 {S(C 6 H 3 -2-CH 2 NRR′-5-t Bu)}-κ 2 S,N] (RR′ = C 5 H 10 (5a), C 4 H 8 (5b) Me 2 ( 5c)), respectively. These complexes have been characterized by multinuclear NMR spectroscopy and elemental analysis. Moreover, the molecular structures of 3a,b have been determined by X-ray diffraction methods. Aluminum complexes 3 have been investigated for the ring-opening polymerization (ROP) of L-lactide, achieving high conversions in relatively short periods of time. The PLAs obtained feature an aminoarenethiolate end functionality, as inferred from MALDI-TOF mass analysis.