The synthesis, IR spectrum, and first-principles characterization of CF3CH(ONO)CF3 as well as its use as an OH radical source in kinetic and mechanistic studies are reported. CF3CH(ONO)CF3 exists in two conformers corresponding to rotation about the RCO-NO bond. The more prevalent trans conformer accounts for the prominent IR absorption features at frequencies (cm(-1)) of 1766 (N=O stretch), 1302, 12 10, and 1119 (C-F stretches), and 761 (O-N-O bend); the cis conformer contributes a number of distinct weaker features. CF3CH(ONO)CF3 was readily photolyzed using fluorescent blacklamps to generate CF3C(O)CF3 and, by implication, OH radicals in 100% yield. CF3CH(ONO)CF3 photolysis is a convenient source of OH radicals in the studies of the yields of CO, CO2, HCHO, and HC(O)OH products which can be difficult to measure using more conventional OH radical sources (e.g., CH3ONO photolysis). CF3CH(ONO)CF3 photolysis was used to measure k(OH + C2H4)/k(OH + C3H6) = 0.29 +/- 0.01 and to establish upper limits of 16 and 6% for the molar yields of CO and HC(O)OH from the reaction of OH radicals with benzene in 700 Torr of air at 296 K. (C) 2003 Wiley Periodicals, Inc.