In this study, a general procedure was proposed for synthesizing thioethers and selenide ethers from anilines under solvent-free and transition-metal-free conditions. Thioethers were formed when anilines reacted with thiols under blue light-emitting-diode (LED) irradiation at room temperature without a photocatalyst. When reactions were performed using anilines and diselenides, the corresponding selenide ethers were obtained with satisfactory to excellent yields. The reaction was performed under photocatalyst-free and solvent-free conditions without blue LEDs. The advantages of this system include convenient operations, mild reaction conditions, satisfactory functional group tolerance, and late-stage selenylation of drug molecules.