AbstractPhotosynthetic capacity (leaf maximum carboxylation rate, Vcmax) is a critical parameter for accurately assessing carbon assimilation by plant canopies. Recent studies of sun-induced chlorophyll fluorescence (SIF) have shown potential for estimating Vcmax at the ecosystem level. However, the relationship between SIF and Vcmax at the leaf and canopy levels is still poorly understood. In this study, we investigated the dynamic relationship between SIF and Vcmax and its controlling factors using SIF and CO2 response measurements in a rice paddy. We found that SIF and its yield (SIFy) were strongly correlated with Vcmax during the growing season, although the relationship varied with plant growth stages. After flowering, SIFy showed a stronger relationship with Vcmax than SIF flux at both the leaf and canopy levels. Further analysis suggested that the divergence of the link between SIF and Vcmax from leaf to canopy are the result of changes in canopy structure and leaf physiology, highlighting that these need to be considered when interpreting the SIF signal across spatial scales. Our results provide evidence that remotely sensed SIF observations can be used to track seasonal variations in Vcmax at the leaf and canopy levels.