In this chapter, we focus on the benefits LIBS offers when it comes to the characterization of polymer samples. LIBS is usually considered an analytical technique used for elemental analysis to detect all elements of the periodic table. Besides elemental information, under certain circumstances, LIBS can also provide molecular information from the sample under investigation, originating either from incomplete atomization or recombination in the laser-induced plasma. The molecular information (e.g., C2, CN, OH, etc.) combined with the possibility of directly detecting the main common constituents of polymers C, H, N, and O proves to be beneficial for specific fields of polymer characterization. Using the information obtained from LIBS spectra combined with the unique capabilities of LIBS (e.g., imaging, depth profiling, online measurements, lack of sample preparation) results in an analytical technique with powerful characteristics for polymer analysis. We also present topics where a lot of research is focused on developing novel applications of LIBS for polymer analysis, highlighting the benefits of this technique.