Absorption and fluorescence spectroscopy studies reveal the formation of a weak complex between pyrene and C6F6 even in very dilute systems. The complex affects the photophysics of pyrene and reveals a combination of static and dynamic-quenching phenomena in both polar and nonpolar solvents. The results are supported by computational studies that shed light on the structure of the complex and the interactions involved and suggest that ground and excited-state interactions are of comparable magnitude; the association is believed to be driven by quadrupolar interactions. Understanding these interactions in solution is important for applications that aim at controlling the regio- or stereoselectivity of organic reactions.