This study was performed on scalp hair samples from postmenopausal women (n=26; 12 normotensives and 14 hypertensives) to determine the relationship between blood pressure and metal and metalloids in hair samples. Hair concentrations of Al, Ba, Cd, Co, Cr, Mn, Mo, Ni, Pb, Sb, Se, Sr and V were measured using inductively coupled plasma mass spectrometry, whereas Ca, Cu, Fe, K, Mg, Na and Zn concentrations were measured by inductively coupled plasma optical emission spectrometry. Methods were optimized and then validated using certified reference material GBW 09101 human hair. Although Cd, Co and Mo levels in hypertensive volunteers were significantly higher than in normotensive individuals (P<0.05), the concentrations of Fe, Mn, Na (all P<0.05) and K (P<0.001) were significantly lower. Concentrations of K (P<0.001; P<0.001) were negatively correlated with systolic and diastolic blood pressure. The concentration of Co (P=0.004; P<0.001) displayed a positive correlation with both types of pressure, whereas Cu (P=0.013) and Ni (P<0.001) concentrations correlated significantly with diastolic blood pressure and Mn negatively correlated with systolic blood pressure (P=0.031). Overweight and hypertension concurred in 27% of volunteers. This concurrence did not modify differences in hair mineral levels attributed to hypertension. The present results indicate that scalp hair concentrations of certain metals and metalloids can be used as biomarkers for hypertension in postmenopausal women.