Arsenic, cadmium and lead in aerosols, dusts and surface soils from Australia's oldest continuous lead mining town of Broken Hill were compared to standardised national childhood developmental (year 1) and education performance measures (years 3,5,7,9). Contaminants close to mining operations were elevated with maximum lead levels in soil: 8900 mg/kg; dust wipe: 86,061 μg/m2; dust deposition: 2950 μg/m2/day; aerosols: 0.707 μg/m3. The proportion of children from Broken Hill central, the area with the highest environmental contamination, presented with vulnerabilities in two or more developmental areas at 2.6 times the national average. Compared with other school catchments of Broken Hill, children in years 3 and 5 from the most contaminated school catchment returned consistently the lowest educational scores. By contrast, children living and attending schools associated with lower environmental contamination levels recorded higher school scores and lower developmental vulnerabilities. Similar results were identified in Australia's two other major lead mining and smelting cities of Port Pirie and Mount Isa.