Abstract2‐(1‐Hydroxyethylidene)malononitrile (4) is commercially sold as the keto isomer and is described in the literature as either a keto (4 b) or enol (4 a) species. Using NMR techniques and single crystal X‐ray diffraction, we were able to show that 4 exists exclusively as the enol isomer (4 a) in solution as well as in the solid state, which agrees with quantum chemical calculations. By adding one or two equivalents of the Lewis acid B(C6F5)3, the mono‐ or diadducts are formed in exergonic reactions, in which the enol form is further thermodynamically stabilized. The structure and acidity of enol 4 a and its borane adducts are discussed based on experimental and theoretical results.