The population of the semi-arid areas of the countries in the East African Rift Valley (EARV) is faced with serious problems associated with the availability and the quality of the drinking water. In these areas, the drinking water supply largely relies on groundwater characterised by elevated fluoride concentration (> 1.5 mg/L), resulting from interactions with the surrounding alkaline volcanic rocks. This geochemical anomaly is often associated with the presence of other naturally occurring potentially toxic elements (PTEs), such as As, Mo, U, V, which are known to cause adverse effects on human health. This study reports on the occurrence of such PTEs in the groundwater on the populated flanks of Mt. Meru, an active volcano situated in the EARV. Our results show that the majority of analysed PTEs (Al, As, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Se, Sr, Pb, and Zn) are within the acceptable limits for drinking purpose in samples collected from wells, springs and tap systems, suggesting that there is no immediate health risk associated with these PTEs. However, some of the samples were found to exceed the WHO tolerance limit for U (> 30 μg/L) and Mo (> 70 μg/L). The sample analysis also revealed that in some of the collected samples, the concentrations of total dissolved solids, Na+ and K+ exceed the permissible limits. The concerning levels of major parameters and PTEs were found to be associated with areas covered with debris avalanche deposits on the northeast flank, and volcanic ash and alluvial deposits on the southwest flanks of the volcano. The study highlights the need to extend the range of elements monitored in the regional groundwater and make a more routine measurement of PTEs to ensure drinking water safety and effective water management measures