Despite the vast importance of cassava (Manihot esculenta Crantz) for smallholder farmers in Africa, yields per unit land area have not increased over the past 55 years. Genetic engineering or breeding for increased photosynthetic efficiency may represent a new approach. This requires the understanding of limitations to photosynthesis within existing germplasm. Here, leaf photosynthetic gas exchange, leaf carbon and nitrogen content, and nonstructural carbohydrates content and growth were analyzed in four high‐yielding and farm‐preferred African cultivars: two landraces (TME 7, TME 419) and two improved lines (TMS 98/0581 and TMS 30572). Surprisingly, the two landraces had, on average, 18% higher light‐saturating leaf CO
2 uptake (A
sat) than the improved lines due to higher maximum apparent carboxylation rates of Rubisco carboxylation (V
cmax) and regeneration of ribulose‐1,5‐biphosphate expressed as electron transport rate (J
max). TME 419 also showed a greater intrinsic water use efficiency. Except for the cultivar TMS 30572, photosynthesis in cassava showed a triose phosphate utilization (TPU) limitation at high intercellular [CO
2]. The capacity for TPU in the leaf would not limit photosynthesis rates under current conditions, but without modification would be a barrier to increasing photosynthetic efficiency to levels predicted possible in this crop. The lower capacity of the lines improved through breeding, may perhaps reflect the predominant need, until now, in cassava breeding for improved disease and pest resistance. However, the availability today of equipment for high‐throughput screening of photosynthetic capacity provides a means to select for maintenance or improvement of photosynthetic capacity while also selecting for pest and disease resistance.