We synthesized a new family of IrIII complexes [Ir(R1‐ppy)2(R2‐ppl)](PF6), where R1‐ppy = 2‐phenylpyridine (ppy) or 2,4‐difluorophenylpyridine (F2‐ppy) and R2‐ppl = pyrazino[2,3‐f][1,10]phenanthroline (ppl) or 2,3‐diethoxycarbonylpyrazino [2,3‐f][1,10]phenanthroline (deeppl). The complexes were experimentally and theoretically characterized, noting the importance of the R1 substituent on the modulation of HOMO level and its impact on the electronic properties. These compounds exhibit high second‐order nonlinear optics (NLO) activity, especially, those with F2‐ppy ligands; this substituent modulates the charge transfer, optimizing the NLO response. The compounds also show blueshifted emissions, both in solution and as a solid film, which is desirable for use in light‐emitting devices. This is the first use of the synthesized complexes for application in the two tasks.