Abstract A Fe III ‐triflate complex, bearing a bis‐thioether‐di‐phenolate [OSSO]‐type ligand, was discovered to promote the ring‐opening of glycidol with alcohols under mild reaction conditions (0.05 mol % catalyst and 80 °C). The reaction proceeded with high activity (initial turnover frequency of 1680 h −1 for EtOH) and selectivity (>95 %) toward the formation of twelve monoalkyl glyceryl ethers (MAGEs) in a regioselective fashion (84–96 % yield of the non‐symmetric regioisomer). This synthetic approach allows the conversion of a glycerol‐derived platform molecule (i.e., glycidol) to high‐value‐added products by using an Earth‐crust abundant metal‐based catalyst.