In this study, the evolution of C60F18 molecules on a Cu(001) surface was studied by means of scanning tunneling microscopy and density functional theory calculations. The results showed that fluorinated fullerenes (tortoise-shaped polar C60F18) decay on Cu(001) surfaces by a step-by-step detachment of F atoms from the C60 cage. The most favorable adsorption configuration was realized when the F atoms of C60F18 pointed towards the Cu surface and six F atoms were detached from it. The results also showed that a further decay of C60F12 molecules strongly depended on the initial C60F18 coverage. The detached F atoms initially formed a two-dimensional (2D) gas phase which then slowly transformed into F-induced surface structures. The degree of contact between the C60F12 molecules and the Cu(001) surface depended on the density of the 2D gas phase. Hence, the life-time of fluorinated fullerenes was determined by the density of the 2D gas phase, which was affected by the formation of new F-induced structures and the decay of C60F12 molecules. © 2018, Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature.