The present study analyzed the exposure and risk assessment of 4 toxic (Hg, Cd, As, Tl) and 2 essential (Se, Mo) elements in 119 Spanish women of reproductive age. The focus was on the elements for which risk‐based benchmark, biomonitoring equivalents, or health‐related human biomonitoring values have already been established. All elements presented frequencies of detection of 100% (greater than the limit of detection), except for Cd (99%). The 95th percentile concentrations were, for the toxic metals, 358.37 µg/L (total As), 1.10 µg/L (Cd), 0.41 µg/L (Tl), and 3.03 µg/L (total Hg) and, for the essential elements, 68.95 µg/L (total Se) and 154.67 (Mo). We examined sociodemographic factors and dietary habits of women as predictors of urinary metal concentrations. Arsenic was positively associated with fish, shellfish, and canned fish consumption, whereas Mo was found to be associated with the consumption of cereals and pastry products. Maternal urine levels of As were negatively correlated with gestational age. In a risk‐assessment context, hazard quotients (HQs) using the 95th percentile ranged from 0.08 (Tl) to 15.1 (urinary speciated As), with Cd presenting an HQ of 1.1 (95th percentile). None of the essential metals presented concentrations higher than their upper intake level; however, 3% of the mothers showed lower levels of Se than the estimated average requirement (EAR) biomonitoring equivalent, and 20% of the mothers were found to have lower levels of Mo than the EAR biomonitoring equivalent, suggesting a nutritionally inadequate diet. Environ Toxicol Chem 2021;40:1477–1490. © 2021 SETAC