Azetines, four-membered unsaturated nitrogen-containing heterocycles, hold great potential for drug design and development, but remain underexplored due to challenges associated with their synthesis. We report an efficient, visible light-mediated approach to-wards 1- and 2-azetines relying on alkynes and the unique triplet state reactivity of oximes, specifically 2-isoxazolines. While 2-azetine products are accessible upon intermolecular [2+2]-cycloaddition via triplet energy transfer from a commercially available iridi-um photocatalyst, the selective formation of 1-azetines proceeds upon a second, consecutive, energy transfer process. Mechanistic studies are consistent with a stepwise reaction mechanism via N-O bond homolysis following the second energy transfer event to result in the formation of 1-azetine products. Characteristic for this method is its operational simplicity, mild conditions and modular approach that allows for the synthesis of functionalized azetines and tetrahydrofurans via in situ hydrolysis from readily available precursors.