The synthesis of a new sapphyrin macrocycle, selenasapphyrin, with one of the nitrogen atoms in the inner core replaced by a selenium atom is described. This macrocycle is able to bind anions when protonated and form out-of-plane complexes with certain low-valent transition metal fragments once deprotonated. These chemical properties were confirmed by X-ray diffraction analysis with structures of both the bis(hydrochloride) salt and bis(iridium(I) dicarbonyl) complex being obtained.