Treatment of arylcopper species with strongly coordinating ligands is known to lead to break-down of the aggregated structures. We found that the 1:1 complex of pentafluorophenylcopper with pyridine displays interesting cuprophilic and p-stacking interactions that result in the formation of extended supramolecular structures. This complex was also found to display strong blue luminescence in the solid state. To further examine the structural and photophysical properties of this new class of complexes, the pentafluorophenylcopper tetramer was treated with different substituted pyridine ligands. The coordination of these ligands to copper was confirmed by ¹H, ¹⁹F, ¹³C, NMR spectroscopy and x-ray crystallography. All these complexes show interesting luminescence properties in the solid state at low temperature. The relation between structural properties and photophysical properties was further studied.