Polymers play an important role in materials science, because of their advantages over other types of materials. The huge variety in terms of the types, arrangements and combinations of monomers found in polymers leads to an extremely wide diversity of different polymeric materials. Although there is a wide range of analytical techniques to characterize polymeric materials, here the focus is laid on a novel correlative microscopy method, combining Raman microscopy, scanning electron microscopy (SEM) and energy dispersive X‐ray spectroscopy (EDXS). Therefore, three polymeric specimens were analysed by the new system RISE (Raman Imaging and Scanning Electron microscopy) in combination with EDXS. The aim of this contribution is to demonstrate the potential of the new system to characterize different polymeric layers, as well as fillers and additives in polymeric materials. In addition to the results, a methodical chapter deals with preparation aspects, investigation skills and imaging modes of the electron microscope. Here the so‐called variable pressure mode (VP) is mentioned, where nitrogen is used as imaging gas at pressures between 10 and 133 Pa. Furthermore, the low‐voltage mode in the high vacuum is discussed which gives a better surface resolution due to a smaller interaction volume of the electrons in the material and furthermore causes lower beam damage. Both modes work without a conductive coating on the specimen, which is a requirement for Raman investigations. Further capabilities of the RISE system in combination with the EDXS will be discussed afterwards.