Isolated dianions of highly fluorinated [60]fullerenes have been produced for the first time with direct electrospray ionization (ESI). Stable dianions have been observed by spraying extremely dilute solutions of neutral fluorofullerenes, which may enhance their formation and/or prevent their depletion by the unwanted electron detachment. The formation of C60Fx2- dianions provides a striking example of the electrochemical nature of the ESI process. (c) 2005 Elsevier B.V. All rights reserved.