Henry’s law constant (Kh) of CF₂Br₂ was measured to be 0.058 M atm⁻¹ at room temperature. The steady state as well as laser (248 nm) flash photolysis of CF₂Br₂ was carried out in aqueous solution. The formation of Br2^•− radicals involving two primary photodissociation channels was observed in the flash photolysis. One channel produced CF2Br• and Br^• radicals, and the other led to the formation of Br⁻ and H⁺. The spectrum and reactions of CF₂Br^• were studied in aqueous solution by pulse radiolysis. The CF₂Br^• radical was found to absorb in the 230–270 nm region with a molar absorbance (ε) of 710 M⁻¹ cm⁻¹ at ^λmax = 245 nm. The rate constants of some of the reactions were measured at 299 K as follows: k (e_aq⁻ + CF₂Br₂) = 1.20 ± 0.13 × 1010, 2k (CF₂Br^• + CF²Br^•) = 1.4 ± 0.4 × 109, k(CF₂Br^• + O₂) = 1.9 ± 0.5 × 109 M⁻¹ s⁻¹. The CF₂BrO^2• radical absorbed in the 245–360 nm region with ε = 593 M−1 cm−1 at ^λmax = 265 nm. An apparatus used to measure Kh, and a closed-loop flow system used to carry out the flash photolysis/pulse radiolysis of sparingly soluble gases, like CF₂Br₂, are reported.