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