Herein, we report a general and practical electrochemical method for the synthesis of α-keto esters from malonic acid derivatives via α-carbonyl carbocations. Although these cations are typically unstable, they can be efficiently generated under Hofer-Moest-type conditions when stabilized by an α-acetoxy substituent. This metal- and supporting-electrolyte-free approach grants straightforward access to α-keto esters that are otherwise challenging to obtain using conventional methods.