Concentrations of halogens (fluorine, chlorine, bromine and iodine) were determined in six geochemical reference materials (BHVO-2, GS-N, JG-1, JR-1, JB-1b, JB-2). Halogens were first extracted from powdered samples using a pyrohydrolysis technique, then hydrolysis solutions were analysed by ion chromatography for F and Cl and inductively coupled plasma-mass spectrometry for Br and I. The detection limits in solutions were 100 μg l−1 for both F and Cl and 10 ng l−1 for Br and I. Considering the extraction procedure, performed on a maximum of 500 mg of sample and producing 100 ml of pyrohydrolysis solution, detection limits in rock samples were 20 mg kg−1 for F and Cl and 2 μg kg−1 for Br and I. The mean analytical errors on the studied composition ranges were estimated at 10 mg kg−1 for F and Cl, 100 μg kg−1 for Br and 25 μg kg−1 for I. The concentration values, based on repeated (generally > 10) sample analysis, were in good agreement generally with published values and narrowed the mean dispersion around mean values. Large dispersions are discussed in terms of samples heterogeneity and contaminations during sample preparation. Basaltic RMs were found to be more suitable for studies of halogen compositions than differentiated rock material, especially granites – the powders of which were heterogeneous in halogens at the 500 mg level.