Dicobalt hexacarbonyl complexes are well-known for their applications in the Nicholas reaction or simply as a protecting group for alkynes. To recover the alkyne, demetalation is necessary, which usually involves a stoichiometric amount of an oxidizing agent or a strong ligand. This article reports a demetalation methodology based on a photocatalytic process. This approach employs a photocatalyst under aerobic conditions, and the optimal results were achieved using mild near-infrared irradiation. A mechanistic investigation is also presented to elucidate how the photocatalytic system promotes this deprotection. This tool is compatible with the one-pot reaction and orthogonal deprotection of alkynes, offering new perspectives for further applications.