Abstract: A series of cyclometalated platinum(II) complexes with nitrile and isocyanide ligands (RCN and RNC; R = t-Bu, Bn, Ph) have been synthesized in 60–80% yields from the dimer [{Pt(ppy)Cl}₂] (Hppy is 2-phenylpyridine) and the corresponding nitriles and isocyanides. The structure of the synthesized complexes was determined by mass spectrometry, IR and NMR spectroscopy, and X-ray diffraction. The contributions of different intermolecular interactions to the crystal packing were estimated by Hirshfeld surface analysis. Photophysical properties of the synthesized complexes in solution and solid state were studied.