Metalfluoride anions are produced from reaction of fluorinated fullerenes with activated metal surfaces. Display omitted •Metalfluoride anions are produced from reaction of fluorinated fullerenes with activated metal surfaces.•In a plasma ion source, C60Fx react with the Mo and W of the filament and sample holder yielding MoF5/6− and WF5/6−.•In laser desorption/ionisation (LDI) of C60Fx on Al, Cu and Fe foils, the respective metalfluoride anions are generated.•The metalfluoride yields strongly depend on the fluorine content of the fullerene. A comparative investigation into the chemical reactions of a series of fluorinated fullerenes (C60F18, C60F36 and C60F48) with a variety of activated metal surfaces is reported. New ways of generating intense beams of metal fluoride anions are demonstrated: either in reactions of fluorinated fullerene vapours with hot W and Mo metal surfaces in a plasma ion source or by laser desorption/ionisation (LDI) of solid fluorinated fullerenes from various metal substrates (Al, Fe, Cu, Pt, W). In both cases, the resulting metal fluorides and their anions are formed in the highest oxidation state, yielding molybdenum and tungsten hexafluoride anions (plasma ion source), aluminium and iron tetrafluoride anions, and copper trifluoride anions (LDI). No reactions were observed with Pt and W in LDI. The reactivity of the metals towards fluorination correlates with their positions in the metal activity series. Relative yields of bare metal cations are dictated by their ionisation energy. The yield of metal fluoride anions is strongly dependent on the fluorine content of the fluorofullerenes.