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In this communication we report the synthesis and the characterization of the first solid and air‐stable selenolates, starting from commercially available phenylselenenyl halides and elemental zinc. These reagents were efficiently employed in the ring opening of epoxides as well as in other nucleophilic substitution and addition reactions showing an unexpected rate acceleration in water suspension at room temperature. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)