We report the preparation of alkali and alkaline earth (Ae) metal complexes supported by 2-picolylamino-diphenylphosphane chalcogenide [(Ph2P(=E)NHCH2(C5H4N)] [E = S (1-H); Se (2-H)] ligands. The treatment of the protic ligand, 1-H or 2-H, with alkali metal hexamethyldisilazides at room temperature afforded the corresponding alkali metal salts [M(THF)2(Ph2P(=E)NCH2(C5H4N)] [M = Li, E = S (3a), Se (3b)] and [{M(THF)n(Ph2P(=E)NCH2(C5H4N)}2] [M = Na, E = S (4a), Se (4b); M = K, E = Se (5b)] in good yield. The homoleptic Ae metal complexes [κ2-(Ph2P(=Se)NCH2(C5H4N)Mg(THF)] (6b) and [κ3-{(Ph2P(=Se)NCH2(C5H4N)}2M(THF)n] (M = Ca (7b), Sr (8b), Ba (9b)] were synthesized by the one-pot reaction of 2-H with [KN(SiMe3)2] and MI2 in a 2:2:1 molar ratio at room temperature. The molecular structures of the protic-ligands 1-H and 2-H, as well as complexes 3a,b-5a,b and 6b-9b were established using single-crystal X-ray analysis. The Ae metal complexes 6b-9b were tested for ring-opening polymerization (ROP) of racemic lactide (rac-LA) and copolymerization of rac-LA and ϵ-caprolactone (ϵ-CL) at room temperature. In the ROP of rac-LA, the calcium complex 7b exhibited high isoselectivity, with Pi = 0.89, whereas both the barium and strontium complexes showed lower isoselectivity with Pi = 0.78-0.62. In the copolymerization of rac-LA and ϵ-CL, both barium and strontium complexes proved to be efficient precatalysts for the formation of the block copolymer rac-LA-CL, but the reactivity of 9b was found to be better than that of 8b. All the polymers were fully characterized using differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography analyses. Kinetic studies on the ROP reaction of LA confirmed that the rate of polymerization followed the order Ba ≥ Sr ≈ Ca. © 2018 American Chemical Society.