Sedum plumbizincicola is a zinc-cadmium (Zn-Cd) hyperaccumulator native to China with high potential for use in phytoremediation of contaminated soils in temperate climate. This study aimed to determine the Zn accumulation and distribution in S. plumbizincicola tissues grown on soils co-contaminated with Cd, Pb and Zn. The efficiency of Zn accumulation was assessed in a monoculture and in co-cropping systems with Noccaea caerulescens. The samples were analysed by inductively coupled plasma–atomic emission spectrometry and synchrotron micro-X-ray fluorescence elemental imaging. Sedum plumbizincicola grown in monoculture showed significantly higher foliar concentrations of Zn than the plants grown with N. caerulescens, with the leaf tips, petioles and nodes being the main sites of Zn localisation in the aerial parts. The highest Zn concentrations were observed in the epidermis and vascular system, of both leaves and stems, with distribution pattern differing in young and in mature leaves. This study highlights the Zn localisation patterns in S. plumbizincicola to improve our understanding of the mechanisms of hyperaccumulation. Growing in monoculture, S. plumbizincicola is an effective candidate for Zn phytoremediation in contaminated soils, with less promising results when co-cropped with the Ganges ecotype of N. caerulescens.