In this study, we conducted precise measurements to determine the bond dissociation energy of F2, yielding a value of 12939.95 ± 0.40 cm-1 or 154.7962 ± 0.0048 kJ/mol. Our research addresses this currently debated benchmark parameter crucial in thermochemistry and quantum chemistry. By analyzing a rotationally resolved spectrum of an ion-pair state close to the threshold of F(2P3/2°) + F(2P3/2) in the energy region of 14.6 eV, we made a significant observation. We discovered two neighboring rotational states with and without predissociation to the channel, exhibiting an energy spacing of 1.4 cm-1 only. This enabled us to determine the bond dissociation energy of F2 with an uncertainty of 0.7 cm-1, which was further reduced to 0.4 cm-1 using threshold fragment yield spectra of F(2P3/2). Consequently, the accuracy of the F2 bond dissociation energy now surpasses 0.5 cm-1, placing it with similar precision to those of N2, O2, and CO.