The association of arbuscular mycorrhizal fungi (AMF) with the roots of Lindenbergia philippensis (Cham.) Benth., sampled from a Zn-contaminated settling pond at a zinc smelter, significantly enhanced Zn accumulation (72,540 ± 5,092 mg kg dry weight) in rhizosphere sediment amended with 1,000 mg L of Zn sulfate solution compared to fungicide-treatments that suppressed AMF colonization. This can be explained by a significant proportion of Zn being found in rectangular crystals that were associated with the root mucilaginous sheath. Despite this, all treatments maintained the same Zn coordination geometry in both Zn oxidation state and the coordinated neighbouring atoms. X-ray absorption spectroscopy (XAS) showed a Zn(II) oxidation state as a core atom and associated with six oxygen atoms symmetrically arranged in an octahedral coordination and coordinated with sulfur. The results may indicate a role for AMF in enhancing Zn immobilization in the rhizosphere of indigenous plants that successfully colonize Zn mining and smelting disposal sites.