We report a novel cluster, [{Pt(C₆F₅)(bzq)}₂Pb(Spy)₂] 1, that displays reversible vapoluminescence to specific organic vapours; this behaviour can be related to the stereochemical activity of the lone pair around the Pb^II in the ground state and to the distinct distortion of the coordination environment (1 and 1–solvent) upon photoexcitation.