The 1st PROBE programme for the assessment of the internal dose of metals of the Italian population closed in 2011. A population sample of 1423 individuals, aged between 18 and 65 years from five regions, are recruited and information on gender, age and lifestyles of subjects is collected by a questionnaire. Concentrations of 20 metals, namely As, Be, Cd, Co, Cr, Hg, Ir, Mn, Mo, Ni, Pb, Pd, Pt, Rh, Sb, Sn, Tl, U, V and W are determined by the sector field inductively coupled plasma mass spectrometry (HR–ICP–MS) in whole blood and serum. Metals levels are reported as geometric means (GM) and 95th percentiles (P95). Biomarkers variations in sub-groups of the population stratified for influencing variables are also assessed. A comparison with available guideline values for some biomarkers of exposure (Cd, Co, Hg and Pb in human blood) and the levels determined in the Italian population are also outlined.