A new cyclometalated platinum(II) complex [Pt(ppy)(SCN)(CNC6H3-2-F-4-I)] (I, Hppy = 2-phenylpyridine) containing a thiocyanate and an isocyanide ligand is prepared and structurally characterized, its photophysical properties are studied. Complex I in a CDCl3 solution exists as an equilibrium mixture of S- and N-coordinated isomers. In the solid phase, only the N-isomer forming the I & centerdot;CHCl3 (CCDC 2515278) and I & centerdot;CH2Cl2 (CCDC 2515279) solvate is detected upon crystallization from CHCl3 or CH2Cl2. In crystals, molecules of I form supramolecular chains stabilized by short Pt & ctdot;Pt metallophilic contacts and I & ctdot;S halogen bonds. Complex I exhibits green-yellow luminescence in the solution and red excimer emission in the solid state.