We report recent results on the nonradiative decay (NRD) of fluoren-9-ylidene malononitrile (FM) ambipolar derivatives (FMDs). 2,7-and 3,6-disubstituted FMDs present distinctive photophysics. Charge separation was found dominant for excited state relaxation. The radiative decay (RD) is sensitive to changes in temperature and solvent medium only for the case of 3,6-FMDs. Excited state deactivation of carbazole-containing 3,6-FMD (CPAFM36) was exclusively nonradiative in polar solvents with excited state lifetimes shorter than 10 ps. The charge separation/recombination mechanism of the corresponding FMDs is suggested to fall in the inverted Marcus region of electron transfer. Given the electron-withdrawing properties of the FM unit, its ambipolar derivatives are suggested as potential candidates for airstable organic thin-film transistors and molecular organic photovoltaics.