The future capacity of forest ecosystems to sequester atmospheric carbon is likely to be influenced by CO2-mediated shifts in nutrient cycling through changes in litter chemistry, and by interactions with pollutants like O3. We evaluated the independent and interactive effects of elevated CO2 (560 μl l−1) and O3 (55 nl l l−1) on leaf litter decomposition in trembling aspen (Populus tremuloides) and paper birch (Betula papyrifera) at the Aspen free air CO2 enrichment (FACE) site (Wisconsin, USA). Fumigation treatments consisted of replicated ambient, +CO2, +O3, and +CO2 + O3 FACE rings. We followed mass loss and litter chemistry over 23 months, using reciprocally transplanted litterbags to separate substrate quality from environment effects. Aspen decayed more slowly than birch across all treatment conditions, and changes in decomposition dynamics of both species were driven by shifts in substrate quality rather than by fumigation environment. Aspen litter produced under elevated CO2 decayed more slowly than litter produced under ambient CO2, and this effect was exacerbated by elevated O3. Similarly, birch litter produced under elevated CO2 also decayed more slowly than litter produced under ambient CO2. In contrast to results for aspen, however, elevated O3 accelerated birch decay under ambient CO2, but decelerated decay under enriched CO2. Changes in decomposition rates (k-values) were due to CO2- and O3-mediated shifts in litter quality, particularly levels of carbohydrates, nitrogen, and tannins. These results suggest that in early-successional forests of the future, elevated concentrations of CO2 will likely reduce leaf litter decomposition, although the magnitude of effect will vary among species and in response to interactions with tropospheric O3.