With the fast development of synthetic chemistry, the introduction of functional group into organic molecules has attracted increasing attention. In these reactions, the difunctionalization of unsaturated bonds, traditionally with one nucleophile and one electrophile, is a powerful strategy for the chemical synthesis. In this work, we develop a different path of electrochemical oxidative difunctionalization of diazo compounds with two different nucleophiles. Under metal-free and external oxidant-free conditions, a series of structurally diverse heteroatom-containing compounds hardly synthesized by traditional methods (such as high-value alkoxy-substituted phenylthioacetates, α-thio, α-amino acid derivatives as well as α-amino, β-amino acid derivatives) are obtained in synthetically useful yields. In addition, the procedure exhibits mild reaction conditions, excellent functional-group tolerance and good efficiency on large-scale synthesis. Importantly, the protocol is also amenable to the key intermediate of bioactive molecules in a simple and practical process.