A mild, catalyst‐free electrochemical oxytrifluoromethylation of alkenes has been developed. The procedure is based on the paired electrolysis of sodium triflinate and water in an undivided cell. Anodic oxidation of the triflinate anion generates trifluoromethyl radicals that react with the alkene. Water plays a dual role as oxidant for the cathode and nucleophile. The method has been utilized to prepare a diverse set of 1‐hydroxy‐2‐trifluoromethyl compounds in moderate to excellent yields (27–94 %). Alcohols have also been tested as nucleophiles for this versatile method with moderate yields. Facile recycling of the electrolyte has been demonstrated, and application of electricity avoids the use of stoichiometric amounts of oxidizers in a safe and environmentally benign reaction. Electricity and water are key ingredients in this alkene difunctionalization method. Paired electrolysis of sodium trifluoromethanesulfinate and water in an undivided cell enables a mild, catalyst‐free oxytrifluoromethylation of styrenes. Trapping experiments provide evidence of a mechanism involving three radical intermediates.