AbstractThe accurate estimation of photosynthetic phenology using vegetation indices (VIs) is important for measuring the interannual variation of atmospheric CO2 concentrations, but the relative performances of structural and physiological VIs remain unclear. We found that structural VIs (normalized difference VI, enhanced VI, and near‐infrared reflectance of vegetation) were suitable for estimating the start of the photosynthetically active season in deciduous broadleaf forests using gross primary production measured by FLUXNET as a benchmark, and a physiological VI (chlorophyll/carotenoid index) was better at identifying the end of the photosynthetically active season for deciduous broadleaf forests and both the start and end of season for evergreen needleleaf forests. The divergent performances were rooted in the combined control of structural and physiological regulations of carbon uptake by plants. Most existing studies of photosynthetic phenology have been based on structural VIs, so we suggest revisiting the dynamics of photosynthetic phenology using physiological VIs, which has significant implications on global plant phenology and carbon uptake studies.