The loglinear pattern of respiratory scaling has been studied for over a century, while an increasing number of non-loglinear patterns have been found in the plant kingdom. Several previous studies had attempted to reconcile conflicting patterns from the aspects of statistical approaches and developmental stages of the organisms. However, the underlying enzymatic mechanism was largely ignored. Here, we propose an enzyme-driven law of photosynthetic scaling and test it in typical crop seedlings under different water conditions. The results showed that the key enzyme activity, the relative photosynthetic assimilation and the relative growth rate were all constrained by the available water, and the relationship between these biological traits and the available water supported our predictions. The enzyme-driven law appears to be more suitable to explain the curvature of photosynthetic scaling than the well-established power law, since it provides insight into the biochemical origin of photosynthetic assimilation.