Aims <p>Microbes play a significant role in the biogeochemical cycling of soil phosphorus (P). However, little is known on how P accumulation affects the microbial-driving regulation of soil P forms.</p> Methods <p>This study investigated soil P forms and microbial community structure in the presence or absence of P accumulation using ³¹P-NMR spectroscopy and 16S rRNA high-throughput sequencing, respectively.</p> Results <p>Long-term P accumulation increased available P and orthophosphate, but decreased the proportion of phosphate monoester, phospholipids, DNA-P and pyrophosphate. Meanwhile, the abundant and rare microbial taxa possessed different response to soil P accumulation. As a result, due to the change in soil properties and different sensitivity to soil P content, P accumulation enhanced the alpha diversity indices of microbial community and reduced the relative abundances of <i>Proteobacteria</i> and <i>Actinobacteria</i>. In addition, <i>Bacteroidetes</i>, <i>Firmicutes</i>, <i>Gemmatimonadetes</i>, and <i>Nitrospirae</i> were positively correlated with orthophosphate, but negatively correlated with the P forms of phosphate monoesters, DNA, phospholipids, pyrophosphate, and the abundance of <i>pqq</i>C gene. Among the investigated soil properties, soil organic matter, pH, organic phosphate, and <i>pqq</i>C may dominate the assembly of microbial networks.</p> Conclusions <p>Under P accumulation, rare microbial taxa may play a more important role in the assemble of microbial networks for soil P cycling than the abundant microbes. These findings may help to optimize soil management for an enhancement of P use efficiency.</p>