A method for the polymerization of α-lipoic acid and α-lipoic acid derivatives includes preparing an α-lipoic formulation, exposing the α-lipoic formulation to an aqueous phase and a gaseous phase at a gas/water interface, and allowing the α-lipoic formulation to polymerize at the gas/water interface to form a poly(α-lipoic acid) polymer. The α-lipoic formulation can be an α-lipoic solution of an α-lipoic solute and an organic solvent miscible with water, and can also be an α-lipoic acid or oligomer or polymer thereof in liquid (typically melt) form.