Two new three-branched fluorenylene-vinylene derivatives were synthesized by triple Heck-type or Horner-Wadsworth-Emmons reactions. Their one-photon absorption and fluorescence as well as their two-photon absorption properties are reported. These compounds, which combine very high solubility in organic solvents, high fluorescence quantum yield and giant two-photon absorption cross-sections in the red-NIR region (up to 3660 GM, in the femtosecond regime) are promising candidates for both optical power limiting applications and two-photon laser scanning microscopy.