Ecosystem entropy production is predicted to increase along ecological succession and approach a state of maximum entropy production, but few studies have bridged the gap between theory and data. Here, we explore radiative entropy production in terrestrial ecosystems using measurements from 64 Free/Fair-Use sites in the FLUXNET database, including a successional chronosequence in the Duke Forest in the southeastern United States. Ecosystem radiative entropy production increased then decreased as succession progressed in the Duke Forest ecosystems, and did not exceed 95% of the calculated empirical maximum entropy production in the FLUXNET study sites. Forest vegetation, especially evergreen needleleaf forests characterized by low shortwave albedo and close coupling to the atmosphere, had a significantly higher ratio of radiative entropy production to the empirical maximum entropy production than did croplands and grasslands. Our results demonstrate that ecosystems approach, but do not reach, maximum entropy production and that the relationship between succession and entropy production depends on vegetation characteristics. Future studies should investigate how natural disturbances and anthropogenic management—especially the tendency to shift vegetation to an earlier successional state—alter energy flux and entropy production at the surface-atmosphere interface.