The I2(D′−A′) luminescence in liquid C7F16, C8F18, C9F20, and C12F26 has been observed following irradiation with visible (within the I2 X → B band region) and UV (λ < 300 nm) lasers. The band is shifted by ∼2000 cm−1 to the red relative to the gas phase and is significantly broader (fwhm ≈ 3000 cm−1 vs 500 cm−1 in the gas phase). Two-color excitation of other halogens in CnF2n+2 solvents revealed similarly shifted and strongly broadened D′−A′ bands of Br2, IBr, and BrCl. The stability of the ion-pair states of halogens in room temperature liquids opens new experimental opportunities for condensed phase studies and may be of applied interest considering the increasing industrial applications of perfluorocarbons.