We report the synthesis of a di(1-pyrenyl)-phosphoryl acetophenone ligand containing two pyrenyl moieties linked by a single phosphorus atom. The ligand exhibits solvent-dependent emission: in nonpolar solvents, typical monomeric pyrene emission is observed, whereas in polar solvents, an additional broad and structureless emission appears. The emission in polar solvents is concentration independent and is attributed to the emission of an intramolecular excimer. The coordination of the di(1-pyrenyl)phosphoryl acetophenone ligand as well as the corresponding deprotonated anionic di(1-pyrenyl)phosphoryl acetophenonate ligand was studied with the near-infrared emitting lanthanides, neodymium and ytterbium. Solvent-dependent sensitization of both lanthanides was observed and correlates with the presence of the excimer emission. Sensitization of ytterbium is more efficient than neodymium, and the overall quantum yields were found to be 12.8 and 1.9% for ytterbium and neodymium, respectively.