AbstractTetrabutylammonium‐bromide promoted, ytterbium triflate catalyzed one‐pot domino synthesis of spirooxindoles is described. The hydration‐condensation of alkyne, 1 aldehyde, 2 C−C coupling followed by 1,3‐dipolar cycloaddition of in‐situ generated azomethine ylide from Isatin, 3 and L‐proline, 4 a or sarcosine, 4 b furnished novel spirooxindoles, 5 under solvent‐free green‐chemical conditions, in high regio and stereo selectivities and yields. The regio and stereochemistry of the synthesized derivatives were characterized by 2D NMR Spectroscopic studies.