The Doppler-free two-photon excitation spectrum of the vibrationless Ã1B1←Image 1A1 transition of difluorodiazirine (F2CN2) has been recorded with a resolution of 15 MHz using a cw single-mode dye laser coupled to an external concentric resonator. The asymmetric rotor spectrum has been analysed and more than 350 lines randomly selected from all five branches were assigned in order to fit the ground- and excited-state rotational and quartic centrifugal distortion constants. From the rotational constants the rNN and rFF distances in the ground Image 1A1 and excited Ã1B1 state were determined. The geometry change upon excitation is found to be ΔrNN = 3.89(2) pm and ΔrFF = −4.09(2) pm. No perturbation in the rotational structure of the 000 band has been found. This points to a small singlet-triplet coupling matrix element in the small molecule limit.