The concentrations of fluorine, chlorine, bromine and iodine of seven geochemical reference samples have been determined. Analytical techniques were neutron activation analysis for chlorine, bromine and iodine and ion‐selective potentiometry for fluorine. After irradiation of the samples, these halogens were separated from the matrix elements by pyrohydrolysis in presence of vanadium (V) oxide. This extraction allows to measure the four halogens in the same sampl