Abstract 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 (eaq− + 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 CF2BrO2• 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.