A powerful electrophilic activator for organotellurium compounds was developed. Phenyltellanyl triflate (PhTeOTf) prepared in situ from dibromophenyl(phenyltellanyl)telluride and AgOTf selectively activated various organotellurium compounds in the presence of aromatic compounds yielding the corresponding Friedel–Crafts reaction products. Polymer-end organotellurium compounds were also activated by PhTeOTf providing the corresponding end-functionalized polymers.