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The roots of hyperaccumulators can significantly alter soil pH and thus change the chromium (Cr) availability in the rhizosphere. The pH dynamics in the rhizosphere of Cr hyperaccumulator Leersia hexandra Swartz remains unknown. In this study, the spatial dynamics of pH in the rhizosphere of L. hexandra at different Cr exposure were examined using planar optode (PO). The effects of different Cr concentrations on the biomass, physiological parameters, and soil enzyme activity were investigated. The results showed that pH in the rhizosphere of L. hexandra was highly heterogeneous and followed the root shape. There were obvious soil acidification in all groups and the average pH values in the control, Cr50, and Cr100 groups decreased by 0.26, 0.27, and 0.35 pH unit, respectively. At a certain concentration (50 mg kg–1), Cr significantly increased the plant height and biomass of L. hexandra compared to the control (p < 0.05). The concentrations of chlorophyll a, chlorophyll b, and total chlorophyll in the leaves increased with increasing Cr concentrations. The acid phosphatase, urease, and catalase activities in the rhizosphere were higher than those in the bulk soil. These results provide new insights into elucidating the hyperaccumulating mechanism of Cr and improving the phytoremediation efficiency.