A new family consisting of three luminescent neutral Ir(III) complexes with the unprecedented [Ir(C boolean AND N boolean AND C)(N boolean AND N)C1] architecture, where C boolean AND N boolean AND C is a bis(six-membered) chelating tridentate tripod ligand derived from 2-benzhydrylpyridine (bnpy) and NAN is 4,4'-di-tert-butyl-2,2'-bipyridine (dtBubpy), is reported. X-ray crystallography reveals an unexpected and unusual double C-H bond activation of the two distal nonconjugated phenyl rings of the bnpy coupled with a very short Ir C1 bond trans to the pyridine of the bnpy ligand. Depending on the substitution on the bnpy ligand, phosphorescence, ranging from yellow to red, is observed in dichloromethane solution. A combined study using density functional theory (DFT) and time-dependent DFT (TD-DFT) corroborates the mixed charge-transfer nature of the related excited states.