In arid regions, biomes particularly responsive to climate change, mosses play an important biogeochemical role as key components of biocrusts. Using the biocrust moss Syntrichia caninervis collected from the Nevada Desert Free Air CO2 Enrichment Facility, we examined the physiological effects of 10 years of exposure to elevated CO2, and the effect of high temperature events on the photosynthetic performance of moss grown in CO2-enriched air. Moss exposed to elevated CO2 exhibited a 46% decrease in chlorophyll, a 20% increase in carbon and no difference in either nitrogen content or photosynthetic performance. However, when subjected to high temperatures (35–40°C), mosses from the elevated CO2 environment showed higher photosynthetic performance and photosystem II (PSII) efficiency compared to those grown in ambient conditions, potentially reflective of a shift in nitrogen allocation to components that offer a higher resistance of PSII to heat stress. This result suggests that mosses may respond to climate change in markedly different ways than vascular plants, and observed CO2-induced photosynthetic thermotolerance in S. caninervis will likely have consequences for future desert biogeochemistry.