Increased availability of soil phosphorus (P) has recently been recognised as an underlying driving factor for the positive relationship between plant diversity and ecosystem function. The effects of plant diversity on the bioavailable forms of P involved in biologically mediated rhizospheric processes and how the link between plant and soil microbial diversity facilitates soil P bioavailability, however, remain poorly understood. This study quantified four forms of bioavailable P (CaCl₂‐P, citric‐P, enzyme‐P and HCl‐P) in mature subtropical forests using a novel biologically based approach, which emulates how rhizospheric processes influence the release and supply of available P. Soil microbial diversity was measured by Illumina high‐throughput sequencing. Our results suggest that tree species richness significantly affects soil microbial diversity (p < 0.05), increases litter decomposition, fine‐root biomass and length and soil organic carbon and thus increases the four forms of bioavailable P. A structural equation model that links plants, soil microbes and P forms indicated that soil bacterial and fungal diversity play dominant roles in mediating the effects of tree species richness on soil P bioavailability. An increase in the biodiversity of plants, soil bacteria and fungi could maintain soil P bioavailability and alleviate soil P limitations. Our results imply that biodiversity strengthens plant and soil feedback and increases P recycling. A plain language summary is available for this article.