The electron probe microanalyzer is a device often used in the field of geology or in the glass and steel industries. However, it is barely known or used in the polymer field. Thus, in this paper, we investigate the use of electron probe microanalyzer for polymer microanalyses and compared it with a scanning electron microscope equipped with an energy dispersive spectrometer. To show the unique potential of this technique only develop in our lab for polymer application, three different samples were studied: (i) a fire protective epoxy-based coating submitted to aging in salt water, (ii) the distribution of organometallic catalysts into a thermal isolative silicone polymer, and (iii) the fouling growth of milk protein (biopolymer) on a stainless steel surface. Compared to an energy dispersive spectrometer, with an electron probe microanalyzer it is possible to quickly create X-ray mappings of low concentration elements at a good resolution, as well as allowing the interpretation of the mechanism of action for the three samples which was impossible using only an energy dispersive spectrometer because of its too low detection resolution.