We report the synthesis and the characterization of a new cationic iridium(III) complex featuring two 1-(p-methoxyphenyl)-5-methoxybenzimidazole cyclometallating ligands and a dimethylbipyridine ancillary ligand. The complex has been fully characterized by 1D and 2D NMR (1H, 13C, 19F and 31P), elemental analysis and high-resolution mass spectrometry (HRMS). The photoluminescence studies performed in a solution, on amorphous powder and on crystals revealed an unexpected behavior. Indeed, the emission spectra observed in both solution (CH2Cl2) and amorphous powder samples are centered at around 580 nm, whereas in crystals the emission displays a large hypsochromic shift of ∼800 cm-1 (λem = 558 nm). X-ray diffraction experiments, photophysical studies and DFT calculations allow for rationalizing the hypsochromic shift.