An efficient and sustainable electrochemical method for the synthesis of cyclic ethers and acyclic aldehydes from alkanols has been reported. This strategy has been successfully applied to cycloalkanols bearing different ring sizes and different types of nucleophiles. In addition, mechanistic investigations show that the reactions undergo sequential processes, including anodic oxidation, βscission, and nucleophilic addition. This method provides a new synthetic approach to constructing cyclic ethers and terminal aldehydes from cycloalkanols and nucleophiles.