Manganese (Mn) exclusion in the Mn hyperaccumulator pokeweed (Phytolacca americana L.) was investigated. Hydroponic experiments were carried out to observe the responses of pokeweeds continually exposed to high levels of Mn. In this study, crystals were observed to appear firstly on the root hair, and soon after, more crystals appeared on the root surface, and crystals of Mn phosphate were observed to appear on the root surface in a time sequence negatively correlated with the number of leaves treated with 5 mM Mn. Crystals were identified via phase analysis of X-ray diffraction and element analysis, and these white insoluble crystals were identified using XRD to be Mn phosphate, with the molecular formula (Mn,Fe)₃(PO₄)₂·4H₂O. The nutrient solution pH increased from 4.5 to about 5.6 before the crystals appeared. Mn phosphate crystals appeared in all solutions except those without phosphate and emerged earlier in the solutions containing no Fe. Compared with control group, pokeweed accumulated much more Mn in the leaves when treated without phosphate or Fe. The present study suggests that pokeweed can exclude Mn by means of rhizosphere precipitation by phosphate to form Mn phosphate crystals that accumulate on the root surface. Although the detailed mechanism requires further investigation, this study provides the first direct evidence of a novel strategy to inhibit Mn uptake in the roots of a hyperaccumulator in a P-enriched environment.