Abstract In this work, a visible‐light‐induced oxidative α‐alkylation of glycine derivatives with ethers has been developed in the presence of catalytic Eosin Y. Under the blue light of a 3 W LED, a range of α‐etherized glycine derivatives, including α‐amino esters, α‐amino ketones and α‐amino amides, were achieved with good to excellent yields and functional group tolerance with tert ‐butyl hydroperoxide (TBHP) as oxidant at ambient temperature. The operationally easy procedure provides an economical, metal‐free, and mild alternative for the synthesis of the α‐etherized glycine derivatives.