Differences in litter decomposition patterns among mesic, semiarid, and arid grassland ecosystems cannot be accurately explained by variation in temperature, moisture, and litter chemistry alone. We hypothesized that ultraviolet (UV) radiation enhances decomposition in grassland ecosystems via photodegradation, more so in arid compared to mesic ecosystems, and in litter that is more recalcitrant to microbial decomposition (with high compared to low lignin concentrations). In a 2-year field study, we manipulated the amount of UV radiation reaching the litter layer at three grassland sites in Minnesota, Colorado, and New Mexico, USA, that represented mesic, semiarid, and arid grassland ecosystems, respectively. Two common grass leaf litter types of contrasting lignin:N were placed at each site under screens that either passed all solar radiation wavelengths or passed all but UV wavelengths. Decomposition was generally faster when litter was exposed to UV radiation across all three sites. In contrast to our hypothesis, the contribution of photodegradation in the decomposition process was not consistently greater at the more arid sites or for litter with higher lignin content. Additionally, at the most arid site, exposure to UV radiation could not explain decomposition rates that were faster than expected given climate constraints or lack of N immobilization by decomposing litter. Although photodegradation plays an important role in the decomposition process in a wider range of grassland sites than previously documented, it does not fully explain the differences in decomposition rates among grassland ecosystems of contrasting aridity.