A series of luminescent cyclometalated rhodium­(III) complexes have been designed and prepared. The improved luminescence property is realized by the judicious choice of a strong σ-donor cyclometalating ligand with a lower-lying intraligand (IL) state that would raise the d–d excited state and introduction of a lower-lying emissive IL excited state. These complexes exhibit high thermal stability and considerable luminescence quantum yields as high as up to 0.65 in thin film, offering themselves as promising light-emitting materials in OLEDs. Respectable external quantum efficiencies of up to 12.2% and operational half-lifetimes of over 3000 h at 100 cd m–2 have been achieved. This work demonstrates a breakthrough as the first example of an efficient rhodium­(III) emitter for OLED application and opens up a new avenue for diversifying the development of OLED materials with rhodium metal being utilized as phosphors.