Given the versatility and value of the structurally diverse organohalides and CF3-containing compounds in organic synthesis, we reported a green, oxidant-free electrochemical method using undivided electrochemical cells for radical bromination, chlorination and trifluoromethylation-formyloxylation of the various alkenes with readily available halogen radical (NaCl, NaBr), trifluoromethyl radical (CF3SO2Na) sources, and DMF as formyloxylation reagents. The protocol is operationally simple and robust and the Cl-, Br- or CF3- was directly oxidized at the anode, obviating the need for exogenous chemical oxidants.