Ultraviolet resonance Raman spectroscopy (UVRR) is being developed for standoff trace explosives detection. To accomplish this, it is important to develop a deep understanding of the accompanying UV excited photochemistry of explosives, as well as the impact of reactions on the resulting photoproducts. In the work here we used 229 nm excited UVRR spectroscopy to monitor the photochemistry of pentaerythritol tetranitrate (PETN) in acetonitrile. We find that solutions of PETN in CD3CN photodegrade with a quantum yield of 0.08 +/- 0.02, as measured by high performance liquid chromatography (HPLC). The initial step in the 229 nm UV photolysis of PETN in CD3CN is cleavage of an O-NO2 bond to form NO2. The accompanying photoproduct is pentaerythritol trinitrate (PETriN), (CH2ONO2)(3)CCH2OH formed by photolysis of a single O-NO2. The resulting UVRR spectra show a dominant photoproduct band at similar to 1308 cm(-1), which derives from the symmetric stretch of dissolved NO2. This photoproduct NO2 is hydrolyzed by trace amounts of water, which downshifts this 1308 cm(-1) NO2 Raman band due to the formation of molecular HNO3. The dissociation of HNO3 to NO3- in the presence of additional water results in an intense NO3- symmetric stretching UVRR band at 1044 cm(-1)