We report on the synthesis of a new series of iridium(III) complexes functionalized with various diimine chromophores, together with a facially coordinated dicyclometalated phosphite chelate and a monodentate anionic ancillary. This conceptual design presents a novel strategy in obtaining a new class of iridium(III) diimine complexes without employment of traditional nitrogen-containing polyaromatic cyclometalates. Additionally, we discuss the basic charactersistics of the ground and lower-lying excited states involved, as documented by crystal structural, photophysical studies, and density functional theory calculations. Fabrication of the green-emitting organic light-emitting diodes with one such dopant, [Ir(dbbpy)(tpit)NCS] (2b), where dbbpy and tpit represent di-tert-butyl-2,2'-bipyridine and dicyclometalated triphenylphosphite, respectively, was successfully made, attaining a peak external quantum efficiency (η(ext)), a luminance efficiency (η(l)), and a power efficiency (η(p)) of 14.1%, 46.6 cd A(-1), and 39.9 lm W(-1), respectively.