By combining a pulsed are cluster ion source with a reflection time-of-flight mass spectrometer, we have produced and detected in situ fullerene cations as well as vanadium-carbon cluster cations. The cluster arrival time distributions favor the "fullerene road" mechanism for fullerene growth. The formation of fullerene cations was found to be strongly dependent on the discharge and nozzle conditions. Fullerene C-60(+)/C-70(+) were preferentially produced by optimizing these conditions. Vanadium-carbon cluster cations were produced and detected by using a composite electrode (V2O5/graphite). While the metallocarbohedrene V8C12+ could be produced with a reasonable it intensity, it was not dominant under our experimental conditions.