A two-step protocol has been developed for ether derivatization introducing oxygen-, sulfur-, and carbon-functionalities. The present protocol comprises photochemical chlorination of ethereal C(sp3)–H bond for preparation of chlorinated ethers as common synthetic intermediates, and nucleophilic substitution of the installed chlorine moiety for construction of various ether derivatives. These two reactions can be conducted sequentially in a single flask, thus the newly developed method offers a one-pot and unified procedure for ether derivatization with attachment of various functionalities at the α-position.