A rational combination of photoredox catalyst anthraquinone and hydrogen atom transfer (HAT) catalyst methyl thioglycolate allows for the rapid and straightforward conversion of a range of 2-amidated acetylenic alcohols to multifunctional N,O-spirocycles under visible light irradiation. With oxygen as the sole terminal oxidant, these reactions can be carried out efficiently at room temperature without the involvement of transition metals or strong oxidants. The successful application of this mild catalytic strategy in the late-stage functionalization of bioactive skeletons further highlights its practical value.