Understanding the causes of variation in functional plant traits is a central issue in ecology, particularly in the context of global change. Spectroscopy is increasingly used for rapid and non-destructive estimation of foliar traits, but few studies have evaluated its accuracy when assessing phenotypic variation in multiple traits. Working with 24 chemical and physical leaf traits of six European tree species growing on strongly contrasting soil types (i.e. deep alluvium versus nearby shallow chalk), we asked (i) whether variability in leaf traits is greater between tree species or soil type, and (ii) whether field spectroscopy is effective at predicting intraspecific variation in leaf traits as well as interspecific differences. Analysis of variance showed that interspecific differences in traits were generally much stronger than intraspecific differences related to soil type, accounting for 25% versus 5% of total trait variation, respectively. Structural traits, phenolic defences and pigments were barely affected by soil type. In contrast, foliar concentrations of rock-derived nutrients did vary: P and K concentrations were lower on chalk than alluvial soils, while Ca, Mg, B, Mn and Zn concentrations were all higher, consistent with the findings of previous ecological studies. Foliar traits were predicted from 400 to 2500nm reflectance spectra collected by field spectroscopy using partial least square regression, a method that is commonly employed in chemometrics. Pigments were best modelled using reflectance data from the visible region (400-700nm), while all other traits were best modelled using reflectance data from the shortwave infrared region (1100-2500nm). Spectroscopy delivered accurate predictions of species-level variation in traits. However, it was ineffective at detecting intraspecific variation in rock-derived nutrients (with the notable exception of P). The explanation for this failure is that rock-derived elements do not have absorption features in the 400-2500nm region, and their estimation is indirect, relying on elemental concentrations covarying with structural traits that do have absorption features in that spectral region (constellation effects). Since the structural traits did not vary with soil type, it was impossible for our regression models to predict intraspecific variation in rock-derived nutrients via constellation effects. This study demonstrates the value of spectroscopy for rapid, non-destructive estimation of foliar traits across species, but highlights problems with predicting intraspecific variation indirectly. We discuss the implications of these findings for mapping functional traits by airborne imaging spectroscopy.