The ecosystem’s gross primary productivity (GPP) and greenness, as indicated by the normalized difference vegetation index (NDVI), are both essential ecological indicators used to evaluate how ecosystems responded to climate variability. However, the relationships between NDVI and GPP under the influence of drying and wetting and its characteristics along aridity (AI) gradients were not yet fully understood. In this study, we investigated the relationships of the NDVI-GPP (i.e., the strength of the coupling and the sensitivity, as quantified by the coefficient of determination (R²) and slope of the linear regression, respectively) along the aridity gradients during the growing season from 1982 to 2018 in China. The results show that the coupling between NDVI and GPP was stronger (i.e., high R²) in semi-arid regions (0.24) compared to humid and hyper-humid regions (R² values were 0.11). For different plant functional types (PFTs), decoupling occurred in ENF with a determination coefficient value (R²) of 0.04, whereas GRA shows a higher coupling with an R² of 0.20. The coupling trend experienced a shift in semi-arid regions, characterized by an aridity index (AI) ranging from 0.20 to 0.50. Additionally, the sensitivity of GPP to NDVI also decreased with increasing aridity. The slope values were 0.19, 0.21, 0.24, 0.20, 0.11, and 0.11 in hyper-arid, arid, semi-arid, dry sub-humid, humid, and hyper-humid, respectively. What is more, asynchronous changes in vegetation productivity and greenness can be detected by capturing the inter-annual variability (IAV) of NDVI and GPP. The IAV of GPP steadily decreased with the aridity gradients, while the IAV of NDVI present fluctuated, suggesting that NDVI was more variable than GPP under the influence of drying and wetting conditions. Our study suggests that there may be a stronger trade-off between ecosystem greenness and photosynthesis in more humid areas.