Dissociative excitation of SF6 by electron impact has been studied under single-collision conditions for incident energies up to 600 eV. The emission spectrum in the spectral range 450–1850 Å shows many features arising from neutral and singly ionized fluorine and sulphur fragments. Absolute cross sections for many of the emissions were measured, and excitation functions and appearance potentials were determined for selected features from each of the four systems. The largest cross sections were found for the FI transitions at 955 Å (2.3 × 10−18 cm2) and 975 Å (1.7 × 10−18 cm2).