The synthesis, electrochemistry, and photophysical properties of a series of bis-cyclometalated Pt(IV) complexes that combine the mesoionic aryl-NHC ligand 4-butyl-3-methyl-1-phenyl-1H-1,2,3-triazol-5-ylidene (trz) with either 1-phenylpyrazole or 2-arylpyridine (C ∧ N) are reported. The complexes (OC-6-54)-[PtCl 2 (C ∧ N)(trz)] bearing cyclometalating 2-arylpyridines present phosphorescent emissions in the blue to yellow color range, which essentially arise from 3 LC(C ∧ N) states, and reach quantum yields of ca. 0.3 in fluid solutions and almost unity in poly(methyl methacrylate) (PMMA) matrices at 298 K, thus representing a class of strong emitters with tunable properties. A systematic comparison with the homologous C 2 -symmetrical species (OC-6-33)-[PtCl 2 (C ∧ N) 2 ], which contains two equal 2-arylpyridine ligands, shows that the introduction of a trz ligand leads to significantly lower nonradiative decay rates and higher quantum efficiencies. Computational calculations substantiate the effect of the carbene ligand, which raises the energy of dσ* orbitals in these derivatives and results in the higher energies of nonemissive deactivating 3 LMCT states. In contrast, the isomers (OC-6-42)-[PtCl 2 (C ∧ N)(trz)] are not luminescent because they present a 3 LMCT state as the lowest triplet.