As a fast-growing, high biomass Cd/Zn co-hyperaccumulating plant, S. alfredii has been identified in China, however the mechanism of Zn hyperaccumulation is not fully understood. In this paper, synchrotron radiation X-ray fluorescence(SRXRF) analysis, together with NPG zinc probe, were employed to assess the distribution of Zn and other elements at cellular level in stems and leaves of HE S. alfredii and its contrasting ecotype. Preferential Zn accumulation in epidermal cells of leaves and stems were observed in both hyperaccumulating and non-hyperaccumulating ecotype of Sedum alfredii, but the former had greater extent. In contrast with the evenly distributed vacuolar sequestration of metals exhibited in the epidermis of most hyperaccumulators, Zn was mainly associated with epicuticular wax, while metal-enriched deposits were also observed in epidermal and subepidermal collenchyma cells in stems for HE S. alfredii. In addition to epidermal enrichment,accumulation of Zn within the vascular bundles of the aboveground tissues was observed in both ecotypes, whereas larger proportion of Zn were restricted in the stem vascular bundles of HE S. alfredii, suggesting that the greater ability of this plant in upwards translocation of excess Zn. Phosphorus (P) was positively responsive to the raising Zn level, and its distribution pattern was also highly consistent with Zn in the shoots of HE S. alfredii, whereas there is absolutely no such relationship between P and Zn in the seedlings of NHE S. alfredii. In contrast to P, Ca was observed to be distributed reversely with Zn.