The maximum light use efficiency (LUE) (ε0) is a key essential parameter of the LUE model, and its accurate estimation is crucial for quantifying gross primary production (GPP) and better understanding the global carbon budget. Currently, a comprehensive understanding of the potential of seasonal variations of ε0 in GPP estimation across different plant functional types (PFTs) is still lacking. In this study, we used a phenology-based strategy for the estimation of ε0 to find the optimal photosynthetic responses of the parameter in different phenological stages. The start and end of growing season (SOS and EOS) from time series vegetation indices and the camera-derived greenness index were extracted across seven PFT flux sites using the methods of the hybrid generalized additive model (HGAM) and double logistic function (DLF). Optimal extractions of SOS and EOS were evaluated, and the ε0 was estimated from flux site observations during the optimal phenological stages with the light response equation. Coupled with other obligatory parameters of the LUE model, phenology-based GPP (GPPphe-based) was estimated over 21 site-years and compared with vegetation photosynthesis model (VPM)-based GPP (GPPVPM) and eddy covariance-measured GPP (GPPEC). Generally, GPPphe-based basically tracked both the seasonal dynamics and inter-annual variation of GPPEC well, especially at forest, cropland, and wetland flux sites. The R2 between GPPphe-based and GPPEC was stable between 0.85 and 0.95 in forest ecosystems, between 0.75 and 0.85 in cropland ecosystems, and around 0.9 in wetland ecosystems. Furthermore, we found that GPPphe-based was significantly improved compared to GPPVPM in cropland, grassland, and wetland ecosystems, implying that phenology-based ε0 is more appropriate in the GPP estimation of herbaceous plants. In addition, we found that GPPphe-based was significantly improved over GPPVPM in cropland, grassland, and wetland ecosystems, and the R2 between GPPphe-based and GPPEC was improved by up to 0.11 in cropland ecosystems and 0.05 in wetland ecosystems compared to GPPVPM, and RMSE was reduced by up to 5.90 and 2.11 g C m−2 8 day−1, respectively, implying that phenology-based ε0 in herbaceous plants is more appropriate for GPP estimation. This work highlights the potential of phenology-based ε0 in understanding the seasonal variation of vegetation photosynthesis and production.