A series of [Ir(C^N) ₂(NN)][PF ₆] complexes in which NN is 5-(4-ethynylphenyl)-2,2′-bipyridine has been synthesized and characterized by spectroscopic methods. All novel complexes exhibit unique singlet-triplet dual emission in solution with two well-separated emission bands. The mechanism of dual emission has been elucidated on the basis of experimental data and confirmed by TDDFT calculations.