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