An efficient and environmentally friendly electrochemical synthesis of phosphorylated oxindoles and indolo[2,1-a]isoquinolin-6(5H)-ones mediated by readily available Cp2Fe has been developed, which illustrated a broad substrate scope and diverse functional group compatibility. This protocol featured an external oxidant-free process and was at room temperature, which was proposed to be driven by the anodic oxidation of Cp2Fe.