Increasing the efficiency of photosynthesis in sugarcane canopies is the key for improving crop yield. Herein, we evaluated the photosynthetic performance along the canopy of ten sugarcane cultivars and three Saccharum species. Canopy morphological traits were evaluated, and leaf gas exchange was measured in the first (sun-exposed, +1) and the fourth (shaded, +4) fully expanded leaves and under low- and high-light conditions. Similar photosynthetic capacity was found in leaves +1 and +4 under high light in genotypes with a high leaf area index and a high fraction of the sky blocked by the foliage (> 85%). Interestingly, such canopy characteristics cause low light availability to leaves +4, suggesting the photosynthetic acclimation of these leaves to self-shading in some genotypes. We highlight IACCTC06-8126 and CTC4 as those genotypes with higher canopy photosynthetic capacity, presenting high leaf area, high photosynthetic rates in sun-exposed leaves, and high responsiveness of shaded leaves to increasing light availability.