AbstractConstruction of chiral quaternary carbon sterocenters especially spirocycles in complex organic molecules is one of the great synthetic challenges. Using a quinine‐derived squaramide catalyst, the enantioselective Michael addition of 4‐amido‐5‐hydroxypyrazoles to ethylene sulfonyl fluoride (ESF) was developed. This method provides a facile strategy to access a series of structurally diverse pyrazolone derivatives with excellent yields and enantioselectivities. The introduction of quaternary carbon stereocenters and sulfonyl fluoride group leads to the valuable candidates for the drug discovery. Furthermore, the products could be transferred to the spirocyclic derivatives under mild reaction conditions without any loss of the enantioselectivities.