The equilibrium molecular structure of the gaseous fluorofullerene C60F36 has been determined for the first time by the electron diffraction method with the use of quantum chemical calculations up to the RI-MP2/def2,-TZVPP level of theory. Vibrational amplitudes and quadratic and cubic force constants were calculated by density functional theory methods. It was found that the sample under study consists of the isomer of C-1 symmetry, 81(4)%, with a small amount of the isomer of C-3 symmetry, in good accordance with HPLC-MS (atmospheric pressure photoionization), HPLC-UV/vis, and NMR spectroscopic data. The presence of the isomer of T symmetry, up to 5%, cannot be completely excluded. Theoretical structural parameters of the C60F36 molecule were compared with those of the C60F48 molecule. Relative to C-61, the C60F36 molecule has a remarkably distorted carbon cage because of steric, electrostatic, and orbital interactions. This results in the longest carbon-carbon bond (1.671 angstrom) found in free molecules. In particular, about the longest FC-CF bond, the dihedral angle is only around 20 degrees, which leads to the very short nonbonded distance between electronegative vicinal fluorine atoms (2.531 angstrom) that is much shorter than the sum of van der Waals radii of fluorine atoms (2.94 angstrom). A natural bond orbital analysis revealed that strong n(pi)(F) -> sigma*(FC-CF) interactions delocalize the lone pair of pi-type at the fluorine atoms into the antibonding orbital of the FC-CF bond. This hyperconjugation results in additional elongation of FC-CF bonds.