Forest functionality and productivity are directly related to canopy light interception and can be affected by potential damage from high irradiance. However, the mechanisms by which leaves adapt to the variable light environments along the multilayer canopy profile are still poorly known. We explored the leaf morphophysiological and metabolic responses to the natural light gradient in a pure European beech (Fagus sylvatica L.) forest at three different canopy heights (top, middle and bottom). Structural adjustment through light-dependent modifications in leaf mass per area was the reason for most of the variations in photosynthetic capacity. The different leaf morphology along the canopy influenced nitrogen (N) partitioning, water- and photosynthetic N-use efficiency, chlorophyll (Chl) fluorescence and quali-quantitative contents of photosynthetic pigments. The Chl a to Chl b ratio and the pool of xanthophyll-cycle pigments (VAZ) increased at the highest irradiance, as well as lutein and β-carotene. The total pool of ascorbate and phenols was higher in leaves of the top and middle canopy layers when compared with the bottom layer, where the ascorbate peroxidase was relatively more activated. The non-photochemical quenching was strongly and positively related to the VAZ/(Chl a + b) ratio, while Chl a/Chl b was related to the photochemical efficiency of photosystem II. Along the multilayer canopy profile, the high energy dissipation capacity of leaves was correlated to an elevated redox potential of antioxidants. The middle layer gave the most relevant contribution to leaf area index and carboxylation capacity of the canopy. In conclusion, a complex interplay among structural, physiological and biochemical traits drives the dynamic leaf acclimation to the natural gradients of variable light environments along the tree canopy profile. The relevant differences observed in leaf traits within the canopy positions of the beech forest should be considered for improving estimation of carbon fluxes in multilayer canopy models of temperate forests.