Laser-induced phosphorescence excitation spectra of SiF2 in the gas phase have been obtained by the pyrolysis jet technique. Vibrational analysis gives a value of v’(2) = 278.2 cm(-1) and ground state vibrational frequencies in good agreement with literature values. The 0(0)(0) band at 380 nm has been recorded with sufficient resolution to observe most of the rotational structure. Rotational analysis establishes that the upper state has B-3(1) symmetry with an r(0) structure of r(SiF) = 1.586 +/- 0.001 Angstrom and angle(FSiF) = 113.1 +/- 0.1 degrees. The upper state spin constants and spin splittings are small, as expected for a nonlinear molecule composed of light atoms. Analysis bf the intensity distribution among the rotational branches in the 0(0)(0) band shows that the triplet-singlet transition gains its intensity primarily by spin-orbit coupling with excited B-1(2) states. A nonradiative decay channel opens up for excited state vibrational energies in excess of two quanta in the bending mode.