AbstractClassical methods for the synthesis of tertiary alcohols mainly rely on the nucleophilic addition of organometallic reagents to carbonyl compounds. Here, we disclose a strategy for synthesizing tertiary alcohols via electroreductive cross‐electrophile coupling of aromatic carbonyl compounds and alkyl bromides (allyl, propargyl, benzyl and cyclohexyl bromides). This procedure features good substrate tolerance and friendly conditions (undivided cell, cheap and reusable carbon electrodes, reaction in open air, room temperature, without any external transition metal/activating reagent). Using this method, 32 desired products can be obtained with moderate to good yields, and gram‐scale synthesis is feasible, demonstrating the practicality of this approach.