The synthesis, luminescence, and nonlinear optical properties of a new series of Ir(ppy)(3) (ppy = 2-phenylpyridine) complexes incorporating pi-extended vinyl-aryl substituents at the para positions of their pyridine rings are reported. Appropriate substitution of the pyridyl rings allows the tuning of the luminescence properties and the second-order nonlinear optical response of this unusual family of three-dimensional chromophores. Theoretical calculations were performed to evaluate the dipole moments, to gain insight into the electronic structure, and to rationalize the observed optical properties of the investigated complexes.