Plant diversity generally promotes biomass production, but how the shape of the response curve changes with time remains unclear. This is a critical knowledge gap because the shape of this relationship indicates the extent to which loss of the first few species will influence biomass production. Using two long-term (≥13 years) biodiversity experiments, we show that the effects of diversity on biomass productivity increased and became less saturating over time. Our analyses suggest that effects of diversity-dependent ecosystem feedbacks and interspecific complementarity accumulate over time, causing high-diversity species combinations that appeared functionally redundant during early years to become more functionally unique through time. Consequently, simplification of diverse ecosystems will likely have greater negative impacts on ecosystem functioning than has been suggested by short-term experiments.