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Phosphorus (P) recovery from wastewater can be completed by iron-involved autotrophic denitrification via forming Fe­(III)–P precipitates and/or adsorbing P onto Fe­(III) oxyhydroxides. However, so far, most studies focused on the final P-containing products, while the P-capturing pathways in such a process remain unclear. In this work, autotrophic iron-dependent denitrification (AIDD) was used as a typical anoxic iron-involved P-capturing biosystem to investigate the main P recovery pathways. The AIDD biosystem showed a relatively stable capability of capturing P coupled with nitrate reduction. Direct formation of amorphous Fe­(II)–P precipitates after the phosphate was fed, followed by microbially driven oxidation into Fe­(III)–P minerals, was found to be the primary pathway for the P capture. In addition, adsorption of phosphate onto the formed iron oxyhydroxides also contributed to the P recovery. This work provides better understanding about recovering P in AIDD and iron-involved denitrification and highlights the important roles of iron oxidizers in the iron-related biological wastewater treatment processes.