Planting diverse forests has been proposed as a means to increase long‐term carbon (C) sequestration while providing many co‐benefits. Positive tree diversity–productivity relationships are well established, suggesting more diverse forests will lead to greater aboveground C sequestration. However, the effects of tree diversity on belowground C storage have the potential to either complement or offset aboveground gains, especially during early stages of afforestation when potential exists for large losses in soil C due to soil decomposition. Thus, experimental tests of the effects of planted tree biodiversity on changes in whole‐ecosystem C balance are needed. Here, we present changes in above‐ and belowground C pools 6 years after the initiation of the Forests and Biodiversity experiment (FAB1), consisting of high‐density plots of one, two, five, or 12 tree species planted in a common garden. The trees included a diverse range of native species, including both needle‐leaf conifer and broadleaf angiosperm species, and both ectomycorrhizal and arbuscular mycorrhizal species. We quantified the effects of species richness, phylogenetic diversity, and functional diversity on aboveground woody C, as well as on mineral soil C accumulation, fine root C, and soil aggregation. Surprisingly, changes in aboveground woody C pools were uncorrelated to changes in mineral soil C pools, suggesting that variation in soil C accumulation was not driven by the quantity of plant litter inputs. Aboveground woody C accumulation was strongly driven by species and functional identity; however, plots with higher species richness and functional diversity accumulated more C in aboveground wood than expected based on monocultures. We also found weak but significant effects of tree species richness, identity, and mycorrhizal type on soil C accumulation. To assess the role of the microbial community in mediating these effects, we further compared changes in soil C pools to phospholipid fatty acid (PLFA) profiles. Soil C pools and accumulation were more strongly correlated with specific microbial clades than with total microbial biomass or plant diversity. Our results highlight rapidly emerging and microbially mediated effects of tree biodiversity on soil C storage in the early years of afforestation that are independent of gains in aboveground woody biomass.