The advantages of LIBS, such as micro-destructivity, high sample throughput, and large amount of acquired information, make the technique attractive for fields of application where quick decision-making is relevant, such as clinical applications or environmental field research. Contrary to possible expectations, atomic spectroscopy can be of service for studies of biological materials no less than molecular (e.g., Raman) spectroscopy. Since the elemental composition of living tissues is highly variable, LIBS has a large potential for qualitative analysis, provided that proper mathematical data treatment is carried out. In this chapter, we have tried to cover achievements in qualitative LIBS-based classification of biological materials (from bacteria to whole multicellular organisms and their tissues), published from 1998 to 2024. Obvious progress has been achieved in the discrimination of bacteria, as well as in the qualitative analysis of plants and food products, which is economically important. This would be impossible without the introduction and popularisation of mathematical (chemometric) algorithms as everyday tools of analytical chemists. Therefore, a short review of popular chemometric methods and tools (PCA, PLS-DA, DFA, SIMCA, SVM, silhouettes, etc.) is included to the chapter. Sometimes chemometrics gets excessive attention to the detriment of experimental and general scientific considerations. However, it may be hoped that, after a critical evaluation of all capabilities and limitations, LIBS-based methods will get regulatory approval and become everyday instruments in biology-related fields, whether it be clinical practice, agriculture, or others.