Abstract A metal‐ and additive‐free multicomponent reaction (MCR) for the synthesis of 3‐oxazoline skeletons is reported. This protocol utilizes readily available α ‐hydroxyketones, ketones, and ammonium salts as substrates, thus overcoming the limitations of existing methods. The reaction exhibits broad substrate tolerance, including cyclic/acyclic ketones, heterocyclic analogs, and various substituted α ‐hydroxyketones, affording polysubstituted 3‐oxazolines in moderate to high yields.