Copper in S.A. primary (NIMROCS) and in six secondary reference samples has accurately been determined by means of atomic absorption spectrometry. A selective ion exchange separation procedure, using a 20 g column of AG50W‐X8 cation exchange resin and 0.2 M hydrochloric acid and 0.5 M hydrobromic acid, both containing 85% acetone, is employed for the separation of copper from all other elements, except vanadium. Vanadium which can partially accompany copper, however, is separated at the start of the sorption step with 0.01 M nitric acid‐0.15% hydrogen peroxide. Accuracy and precision of the described method are demonstrated by the analysis of synthetic rock solutions containing various amounts of copper. Amounts of 10 and 100 μg of copper can be determined with a coefficient of variation of 0.3% and 0.2%, respecti