AbstractThe reaction pathway for the rupture of the carbon–carbon double bond of C2F4 has been calculated with ab initio methods at the CASSCF(8,8)+NEVPT2/aug‐cc‐pVTZ and CCSD(T)/aug‐cc‐pVTZ levels and with density functional theory using M06‐L and M06‐2X functionals in conjunction with aug‐cc‐pVTZ basis sets. The calculations suggest that the bond dissociation pathway proceeds by a nonlinear reaction course without an activation barrier yielding the CF2 fragments in the (1A1) ground state. A bonding analysis indicates that there is a continuous change in the electronic structure of the CF2 fragments during the elongation of the C–C distance from a (3B1) excited state at the equilibrium geometry of C2F4 to the (1A1) ground state. EDA‐NOCV calculations suggest that the carbon–carbon interactions in C2F4 at equilibrium distance and longer C–C values up to ≈1.60 Å are best described in terms of electron‐sharing bonding between the CF2 fragments in the (3B1) excited state. At longer distan