The application of instrumental neutron activation analysis for the determination of long-lived rare earth elements (REE) in rock samples is considered in this work. Two different methods are statistically compared: the well established external standard method carried out using standard reference materials, and the internal standard method (ISM), using Fe, determined through X-ray fluorescence analysis, as an element-comparator. The ISM proved to be the more precise method for a wide range of REE contents and can be recommended for routine practice.