Perfluorodicarbonyl (PFDC) compounds may be emitted directly into the atmosphere or formed in the atmospheric degradation of trace fluorinated gases, such as unsaturated perfluoro cyclic compounds. A potential atmospheric removal process for PFDCs is UV photolysis, which is presently not well-characterized. In this work, UV and infrared absorption spectra of FC­(O)­C­(O)­F, FC­(O)­CF2C­(O)­F, and FC­(O)­CF2CF2C­(O)F (three of the simplest PFDCs) and their 248 nm photolysis products are reported. UV spectra were measured at 296 K between 190 and 320 nm using single wavelength and broadband diode array spectroscopic measurement techniques. Infrared absorption spectra were measured at 296 K using Fourier transform infrared spectroscopy between 500 and 4000 cm–1. The PFDCs are shown to be potent greenhouse gases with radiative efficiencies (well-mixed) of 0.142, 0.218, and 0.293 W m–2 ppb–1 for FC­(O)­C­(O)­F, FC­(O)­CF2C­(O)­F, and FC­(O)­CF2CF2C­(O)­F, respectively. Photolysis product yields (248 nm) were measured using pulsed laser photolysis combined with infrared absorption detection of radical products scavenged to stable bromides by reaction with Br2. BrC­(O)F was identified as a major stable end product in all systems with a yield greater than ∼90%. The infrared spectrum of BrC­(O)F is reported as part of this study. FC­(O)­CBrF2 and FC­(O)­CF2CBrF2 were also identified as products in the photolysis of FC­(O)­CF2C­(O)F and FC­(O)­CF2CF2C­(O)­F, respectively, by comparison with theoretically calculated infrared absorption spectra. A carbonyl difluoride (CF2O) primary photolysis yield of ∼10% was measured in the photolysis of FC­(O)­C­(O)­F.