Demand for critical elements such as In, Sn, Sb, W, and Bi is increasing due to their importance in advanced technologies, renewable energy systems, and strategic industries. However, global supply remains uncertain because many of these metals are produced as by-products, are geographically concentrated, and have declining discovery rates. Reprocessing historical mine waste offers a sustainable alternative by recovering valuable metals without additional mining, while reducing environmental liabilities associated with legacy tailings. This study evaluates mine waste from eight legacy sites within the Herberton Sn–W–Sb–Bi mineral field, Australia, as a secondary resource for In, Sn, Sb, W, and Bi. A multi-scale characterisation workflow integrating bulk geochemistry, automated mineralogy, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and gravity recovery modelling was applied to determine element concentrations, mineral hosts, deportment, and recovery potential. Results reveal significant enrichment of critical elements, with maximum concentrations of In (1155 ppm), Bi (3640 ppm), Sb (53 600 ppm), Sn (81 600 ppm), and W (11 650 ppm). Element deportment varies systematically between samples, reflecting differences in mineralogical composition and weathering history. Lower-grade materials host critical elements primarily within secondary Fe–Sn–Pb–Sb phases, whereas higher-grade materials contain these elements within primary sulfides (chalcopyrite, pyrite, tetrahedrite, sphalerite, and bismuthinite) and Sn–W oxides. Gravity separation modelling predicts potential recoveries of 22–85 per cent In, 53–99 per cent Sn, 26–91 per cent Sb, 13–91 per cent W, and 26–51 per cent Bi. Variations in recovery are primarily associated with mineral liberation, silicate locking, fine grain size distribution, and secondary mineral associations, highlighting the importance of mineralogical controls in selecting appropriate processing pathways. These findings demonstrate the significant potential of historical mine waste in the Herberton mineral field as a secondary source of critical elements. However, variability in mineralogy and liberation characteristics presents challenges for process scalability and economic implementation. Integrating mineralogical characterisation with geometallurgical modelling provides a framework for optimising flow sheet selection, assessing processing limitations, and supporting sustainable circular mineral development.