This study is the first attempt to assess exposure to metals and trace elements in subgroups of the Lebanese population using a multi-matrix biomonitoring approach. Concentrations of 11 metals and trace elements (aluminum (Al), arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), lead (Pb), manganese (Mn), selenium (Se), uranium (U), zinc (Zn)) were measured in urine, hair and toenails. Biological levels were compared according to age, sex, smoking status, socioeconomic status, geographical area and drinking water source. While most urinary and toenail concentrations of metals and trace elements were not different between males and females, measured concentrations of several elements in hair were higher in females compared to males. Urinary concentrations of some metals (Al, Cu, Se and Zn) were higher in children compared to teenagers and adults. Hair and toenail concentrations of several elements (As, Cd, Pb, Mn, Se in hair and toenails plus Al, Fe in toenails) were also significantly higher in children compared to teenagers and/or adults. Smoking status had no influence on metal and trace element concentrations. Levels of Cd, Pb and Mn were also higher in samples from subgroups with lower economic status (Cd and Pb in the three matrices and Mn in hair and toenails). Very few correlations were identified between sources of drinking water and urine, hair, and toenail concentrations of metals and trace elements. However, a correlation was observed between hair and toenails levels of As, Cd and Pb. Overall, results highlight that a special attention should be given to metal and trace element exposure in this population (including Pb, As, Cd, Mn, and Se). It could be relevant to scale up this kind of investigation with a large human biomonitoring initiative in the Lebanese population in order to generalize results, and assess trends over time.