AbstractThe methodology of direct hair analysis by energy‐dispersive x‐ray fluorescence was studied. The effect on the XRF result of having a non‐homogeneous radial distribution of the analyte in a single hair strand and the macroscopic effects in a bundle of hairs were calculated to evaluate possible systematic errors. The detection limits were mapped as a function of the target thickness and surface fraction. It appeared that a 10 mg cm−2sample thickness, i. e. a target with about four layers of hair strands, is recommended. The standard deviation of this simple direct analytical method is 6–19% for some important elements. Discrepancies with neutron activation analysis had a mean value of around 15%. About twelve elements can be determined simultaneously on a rout