Despite the importance of litter decomposition for ecosystem fertility and carbon balance, key uncertainties remain about how this fundamental process is affected by nitrogen (N) availability. Resolving such uncertainties is critical for predicting the ecosystem consequences of increased anthropogenic N deposition. Toward that end, we decomposed green leaves and senesced litter of northern pin oak (Quercus ellipsoidalis) in three forested stands dominated by northern pin oak or white pine (Pinus strobus) to compare effects of substrate N (as it differed between leaves and litter) and externally supplied N (inorganic or organic forms) on decomposition and decomposer community structure and function over four years. Asymptotic decomposition models fit the data equally well as single exponential models and allowed us to compare effects of N on both the initial decomposition rate (ka) and the level of asymptotic mass remaining (A, proportion of mass remaining at which decomposition approaches zero, i.e., the fraction of slowly decomposing litter). In all sites, both substrate N and externally supplied N (regardless of form) accelerated the initial decomposition rate. Faster initial decomposition rates corresponded to higher activity of polysaccharide-degrading enzymes associated with externally supplied N and greater relative abundances of Gram-negative and Gram-positive bacteria associated with green leaves and externally supplied organic N (assessed using phospholipid fatty acid analysis, PLFA). By contrast, later in decomposition, externally supplied N slowed decomposition, increasing the fraction of slowly decomposing litter (A) and reducing lignin-degrading enzyme activity and relative abundances of Gram-negative and Gram-positive bacteria. Higher-N green leaves, on the other hand, had lower levels of A (a smaller slow fraction) than lower-N litter. Contrasting effects of substrate and externally supplied N during later stages of decomposition likely occurred because higher-N leaves also had considerably lower lignin, causing them to decompose more quickly throughout decomposition. In conclusion, elevated atmospheric N deposition in forest ecosystems may have contrasting effects on the dynamics of different soil carbon pools, decreasing mean residence times of active fractions in fresh litter (which would be further reduced if deposition increased litter N concentrations), while increasing those of more slowly decomposing fractions, including more processed litter.