Net ecosystem exchange (NEE) of CO2 is a key process modulating carbon exchanges between terrestrial ecosystems and the atmosphere; however, it remains a grand challenge to elucidate how the interactions of NEE with environmental variables vary among ecosystems and climate regimes across timescales. The FLUXNET and AmeriFlux data sets were used to diagnose the environmental controls on NEE. Based on the sites with long‐term observations (≥7 years), the results showed that the couplings between NEE and surrounding environments were stronger at daily and monthly scales than at annual scales, highlighting the temporal dependence of environmental variables influencing NEE. Moreover, the boosted regression tree method was applied to quantify the relative impacts of environmental controls on daily NEE variations. It revealed that leaf area index (LAI) and shortwave radiation (Rs) were the major divers of daily NEE variations at most sites with the average contribution of 35.5% and 27.8%, respectively. Particularly, LAI was the principal control in deciduous broadleaf forested, non‐forested, and arid sites, while Rs was the leading factor in evergreen forested sites. Meanwhile, air temperature (Ta), soil water content (SWC), and vapor pressure deficit (VPD) exerted smaller influences with the average contribution of 14.6%, 13.2%, and 8.9%, respectively. The relative impacts of LAI, Rs, SWC, and VPD also varied with aridity index, and mean annual precipitation and Ta. Furthermore, NEE was more sensitive to vegetation dynamics in drier climate regions. This study provides additional understanding of how environmental factors regulate NEE dynamics across diverse land surface and climatic conditions.