Single molecule luminophores capable of multiple emissions are essential for the development of new materials with unconventional photophysical behavior. In this work, a family of diphosphine ligands PPh₂-PAH-PPh₂ with variable polyaromatic hydrocarbon (PAH) spacers (PAH = 9,10-anthracene L1, 1,4-naphthalene L2, 2,6-naphthalene L3, and their diethynyl congeners L4-L6) were employed to prepare gold(i) complexes (RC₂Au)PPh₂-PAH-PPh₂(AuC₂R) (1-22), containing a selection of alkynyl groups. Investigation of their optical properties indicates that compounds with anthracene-based diphosphines (1-4 and 13-16) display only ¹IL (ππ∗) fluorescence with Φ_em up to 93%. The naphthalene and diethynyl-naphthalene diphosphine complexes (5-12 and 17-22), however, demonstrate panchromatic emission in the solid state and in solution featuring well-separated low and high energy signals, which originate from ¹IL (ππ∗) and ³IL (ππ∗) transitions along with certain contribution from metal to ligand and ligand to ligand charge transfers.