AbstractA study of the reactivity pattern associated with zwitterionic allenolates “on water” is reported. This study establishes the chemical basis for two organocatalyzed allenolate‐driven reaction networks operating “on water”. The first one is a chemodifferentiating three building block (ABB′) three‐component reaction (ABB′ 3CR) manifold comprising terminal alkynoates and aldehydes. The manifold produces propargylic enol ethers 3 with higher average efficiency than their homologues in organic solvents. The second one is a novel organocatalytic system elicited by the reaction of alkynoates and nitrones in the presence of tertiary amines or phosphines. While terminal alkynoates afford 2,3,5‐trisubstituted 2,3‐dihydroisoxazoles 5 and propargylic N‐hydroxylamines 6, internal alkynoates selectively afford the 2,3,4,5‐tetrasusbstituted 2,3‐dihydroisoxazaole 10. Importantly, in both cases, the 2,3‐dihydroisoxazole ring is obtained as a sole regioisomer.