Theory predicts shifts in the magnitude and direction of biodiversity effects on ecosystem function (BEF) over succession, but this theory remains largely untested. We studied the relationship between aboveground tree biomass dynamics (Δbiomass) and multiple dimensions of biodiversity over 8–16 years in eight successional rainforests. We tested whether successional changes in diversity–Δbiomass correlations reflect predictions of niche theories. Diversity–Δbiomass correlations were positive early but weak later in succession, suggesting saturation of niche space with increasing diversity. Early in succession, phylogenetic diversity and functional diversity in two leaf traits exhibited the strongest positive correlations with Δbiomass, indicating complementarity or positive selection effects. In mid-successional stands, high biodiversity was associated with greater mortality-driven biomass loss, i.e. negative selection effects, suggesting successional niche trade-offs and loss of fast-growing pioneer species. Our results demonstrate that BEF relationships are dynamic across succession, thus successional context is essential to understanding BEF in a given system.