Red and near-infrared (NIR) phosphorescent double-decker dinuclear Pt­(II) complexes were synthesized, and their structural and spectroscopic properties were characterized. The Pt­(II) complexes, which are composed of achiral ligands and are themselves chiral, were shown to exist as racemic mixtures using single-crystal X-ray crystallography. The Pt­(II) complexes have different intramolecular Pt–Pt distances that are governed by the electronic characteristics of the component C^N ligands. Specifically, strengthening of π-back-donation between Pt­(II) and N atom of the C^N ligand leads to shortening of the Pt–Pt distance. The results of both experimental and computational investigations show that the Pt–Pt distances in the dinuclear Pt­(II) complexes significantly influence the band gap energies and corresponding emission wavelengths. Consequently, the uncovered C^N ligand based method to finely control intramolecular Pt–Pt distances in dinuclear Pt­(II) complexes can be utilized as a guideline for the design of the double-decker dinuclear Pt­(II) complexes with red and NIR tuned phosphorescence.