According to recent developments in cement clinker engineering, the optimization of chemical substitutions in the main clinker phases offers a promising approach to improve both reactivity and grindability of clinkers. Thus, monitoring the chemistry of the phases may become part of the quality control at the cement plants, along with the usual measurements of the abundance of the mineralogical phases (quantitative X-ray diffraction) and the bulk chemistry (X-ray fluorescence). This paper presents a new method to assess these three complementary quantities with a single experiment. The method is based on electron microprobe spot analyses, performed over a grid located on a representative surface of the sample and interpreted with advanced statistical tools. This paper describes the method and the experimental program performed on industrial clinkers to establish the accuracy in comparison to conventional methods. (C) 2013 Elsevier Ltd. All rights reserved.