The (A) over tilde(B-1(1))<--(X) over tilde((1)A(1)) electronic transition of difluorocarbene (CF2) has been studied by laser-induced fluorescence spectroscopy in a supersonic free jet and by ab initio theoretical methods. The radical was formed by pyrolysis of C2F4 at similar to 1000 degrees C with a heating chamber at the tip of the nozzle just prior to the gas expansion. Fairly complete rotational cooling, but incomplete vibrational cooling allowed the identification of several new hot band transitions. Ab initio calculations for the (X) over tilde((1)A(1)), (a) over tilde(B-3(1)), and (A) over tilde(B-1(1)) electronic states were performed using the CASSCF method in conjunction with Dunning’s cc-pVTZ basis set, as well as two smaller sets. The calculations allow us to distinguish between several possible assignments of the observed transitions, and hence determine the vibrational frequencies of the two previously unassigned (A) over tilde-state stretching frequencies : nu’(3) = 1180 +/- 2 cm(-1) and nu’(1) = 1011 +/- 2 cm(-1). The ordering of these modes is different from that in the ground state (nu"(1) > nu"(3)) and mechanisms for the switching are discussed.