Accurate spectroellipsometric (SE) measurements in the rotating analyzer (RAE) or rotating polarizer (RPE) configurations require accurate values of the polarizer/analyzer(/retarder) azimuths. While the readings are usually fairly accurate, true values are influenced by possible offsets between the plane of incidence, physical axes of the elements, and the instrument scales. The offsets are often determined by specialized calibration procedures. We describe SE measurements designed to obtain the calibration parameters together with the target ellipsometric spectra. We use multiple settings of the polarizer (analyzer) azimuths in RAE (RPE), respectively, to optimize precision and accuracy of SE measurements, and to economize measurement time. The optimization concerns the choice of measurement parameters as well as the subsequent data analysis. We present in detail examples of visible-ultraviolet measurements. (C) 2010 Elsevier B.V. All rights reserved.