SF₆ is widely used in gas insulated switchgear due to its excellent insulating and arcing performance. SF₆ arc plasma has been extensively studied, but time-resolved spectral characteristics of SF₆ arc plasma have not been reported. In this paper, the optical filament generated from focused femtosecond laser is used to guide the high-voltage discharge for generating SF₆ plasma in SF₆ environment. The SF₆ plasma spectrum is obtained in a wavelength range of 300–820 nm, and the identification and attribution of the spectral lines are investigated. The S and F lines are mainly in the 300–550 nm band and 600–800 nm band, respectively. The analysis shows that the S and F atoms are mainly directly or indirectly generated by the collision between SF₆ and high-energy electrons during the SF₆ decomposition caused by discharge. The S ions are generated by the collision of S atoms with high-energy electrons. The time-resolved spectrum of the SF₆ plasma superimposed by the continuous spectrum and the line spectrum is given, and its intensity increases and then decreases. The continuous spectrum is mainly generated by the combined effect of bremsstrahlung and recombination radiation. The recombination radiation is mainly generated by the collision of electron with ions and the recombination between molecular and atoms after SF₆ decomposition. The fluorescence lifetime of S ion at 409.91 nm is 57 ns, and the fluorescence lifetime of F atom at 685.60 nm is 341 ns. The evolution law of electron temperature and density with time are given. The electron temperature reaches 2047 K in the early stage of plasma formation. After that, the electron temperature quickly falls to about 1600 K within 300 ns due to the rapid expansion of the plasma and the increase in energy loss during electron movement. At the beginning of discharge, a large number of electrons are generated due to the rapid decomposition of SF₆, and the electron density is highest ( $ 10.1 \times {10^{17}}\;{\rm{c}}{{\rm{m}}^{ - {\rm{3}}}}$). After that, the electron density drops rapidly within 200 ns because the recombination between electrons and ions decreases with delay time. Finally, it is proved that the SF₆ plasma is in local thermal equilibrium based on the Mc Whirter criterion. The results are of great significance for studying the decomposition mechanism of SF₆ and the on-line monitoring technique of high-voltage equipment.