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We describe herein a versatile methodology for the synthesis of 1,2‐sulfoximidoyl ethanols thanks to a Ca(NTf2)2‐catalyzed epoxide ring‐opening with NH sulfoximines in 2‐MeTHF at 90 °C. The reaction is regioselective by an attack on the less hindered position of the epoxides. The chemoselectivity is assessed by competition reactions with other nucleophiles.