Tropical rain forests represent some of the most diverse ecosystems on earth, yet mechanistic links between tree species identity and ecosystem function in these forests remains poorly understood. Here, using free-living nitrogen (N) fixation as a model, we explore the idea that interspecies variation in canopy nutrient concentrations may drive significant local-scale variation in biogeochemical processes. Biological N fixation is the largest "natural" source of newly available N to terrestrial ecosystems, and estimates suggest the highest such inputs occur in tropical ecosystems. While patterns of and controls over N fixation in these systems remain poorly known, the data we do have suggest that chemical differences among tree species canopies could affect free-living N fixation rates. In a diverse lowland rain forest in Costa Rica, we established a series of vertical, canopy-to-soil profiles for six common canopy tree species, and we measured free-living N fixation rates and multiple aspects of chemistry of live canopy leaves, senesced canopy leaves, bulk leaf litter, and soil for eight individuals of each tree species. Free-living N fixation rates varied significantly among tree species for all four components, and independent of species identity, rates of N fixation ranged by orders of magnitude along the vertical profile. Our data suggest that variations in phosphorus (P) concentration drove a significant fraction of the observed species-specific variation in free-living N fixation rates within each layer of the vertical profile. Furthermore, our data suggest significant links between canopy and forest floor nutrient concentrations; canopy P was correlated with bulk leaf litter P below individual tree crowns. Thus, canopy chemistry may affect a suite of ecosystem processes not only within the canopy itself, but at and beneath the forest floor as well.