Diarylselenides are a representative class of molecules in organoselenium compounds. We herein report a Rh-catalyzed direct diarylation of selenium with benzamide derivatives. The use of elemental selenium as the Se source is intriguing in terms of atom economy, cost, stability, and handling. A series of diarylselenides with amide moieties were readily accessible through directed C-H activation. The intermediacy of electrophilic Se(IV) species was indicated by control experiments.