The three-component coupling of tertiary amines, arynes, and aryl selenium bromide or diaryl diselenide as an electrophilic selenium source allowing the synthesis of 2-selanyl aniline derivatives is reported. This aminoselenation reaction of arynes installs a C-N and C-Se bond under mild conditions, and the products are formed in moderate to good yields. This reaction is compatible with various functional groups, and the preliminary studies on the mechanism of the reaction is also provided.