Access to homoleptic phosphinine-based coordination compounds of d(6) metals has so far remained elusive. We report here on the preparation and full characterization of the first homoleptic phosphinine-iridium(III) complex, obtained by C-H activation of 2,4,6-triphenylphosphinine with [Ir(acac)(3)]. This result opens up new perspectives for the implementation of such aromatic heterocycles in more applied research fields.