A new PNN-pincer type ligand with pyrazolyl and diphenylphosphine flanking donors on a diarylamido anchor has been prepared. Its bis(tert-butyl isocyanide)rhodium(I) complex exhibits hemilabile behavior in solution, and its solid-state structure verified the elusive (KP)-P-2,N coordination mode for this type of ligand. Reactions between (PNN)Rh((CNBu)-Bu-t)(2) and iodomethane afford both fac- and cis,mer-[(PNN)Rh((CNBu)-Bu-t)(2)(Me)RI), which further showcases the structural versatility of the ligand.