Tree species diversity plays a central role for forest productivity, but factors driving positive biodiversity-productivity relationships remain poorly understood. In a biodiversity experiment manipulating tree diversity and mycorrhizal associations, we examined the roles of above- and belowground processes in modulating wood productivity in young temperate tree communities, as well as potential underlying mechanisms. We found that tree species richness increased forest productivity indirectly by enhancing structural complexity within communities. After six years, structurally complex communities were twice as productive as structurally simple stands. This pattern was consistent across stands with different mycorrhizal associations. Our results also demonstrate that taxonomic diversity and functional variation in shade tolerance, but not phenotypic plasticity, are key drivers of structural complexity in mixtures, which in turn lead to overyielding. Consideration of stand structural complexity appears to be a crucial element in predicting carbon sequestration in the early successional stages of mixed-species forests.