SiF2 has been detected by resonance-enhanced multiphoton ionization mass spectrometry. Two new absorptions have been observed at 481.30 and 379.94 nm and assigned as the (3+1) photoionization via the B̃ 1B2 state and the (1+3) absorption via the ã 3B1 state. A third absorption is observed between 390 and 430 nm which cannot be assigned to any known electronic states of SiF2. Most likely, this is a (3+1) photoionization via a Rydberg state. SiF2 radicals were produced by the reaction of SiF3H with F atoms and by the reaction of F2 with heated silicon crystals under single gas-surface collision conditions.