The synthesis, structure, and photophysical properties of luminescent PtIV complexes that combine cyclometalated 1,2,3‐triazolylidene and bi‐ or terdentate 2,6‐diarylpyridine ligands are reported. The targeted complexes represent the first examples of PtIV species with a cyclometalated mesoionic aryl‐NHC ligand. They exhibit moderate or weak emissions in fluid solution at 298 K arising from 3LC states, which become very intense in poly(methyl methacrylate) (PMMA) matrices at 298 K. DFT and TD‐DFT calculations confirm that the chromophoric ligand is the cyclometalated 2,6‐diarylpyridine and show that the aryl‐NHC ligand exerts a beneficial effect on the emission efficiencies of these derivatives by increasing the energy of deactivating LMCT excited states with respect to comparable PtIV complexes with cyclometalated 2‐arylpyridine ligands.