An electrochemical-enabled three-component cascaded cyclization of enaminones with potassium thiocyanate and alcohols to access 2-alkoxythiazoles has been developed under external oxidant-free conditions. The reaction proceeded smoothly through the electrochemical oxidative C–H thiolation, nucleophilic tandem cyclization to construct the C–O, C–S, and C–N bonds, and the cleavage of the C–N bond. The present protocol afforded a facile and practical approach to various 2-alkoxythiazoles in moderate to good yields from enaminones, thiocyanate and alcohols.