Rapid detection and identification of microorganisms is a challenging and important aspect in many areas of our life, beginning with medicine, ending with industry. Unfortunately, classical methods of microorganisms identification are based on time-consuming and labor-intensive approaches. Screening techniques require rapid and cheap grouping of bacterial isolates; however, modern bioanalytics demands comprehensive bacterial studies on molecular level. The new approach to the rapid identification of bacteria is to use the electromigration techniques, especially capillary zone electrophoresis (CZE). CZE is an important technique used in the analysis of microorganisms. However, the analysis of microbial complexes using this technology still encounters several problems-uncontrolled aggregation and/or adhesion to the capillary surface. One way to resolve this issue is the CZE analysis of microbial cell with surface charge modification by bivalent metal ions (e.g., Ca(2+) aq, Zn aq). Under the above conditions, bacterial cells create compact aggregates, and fewer high-intensity signals are observed in electropherograms. The chapter presents the capillary electrophoresis of microbial aggregates approach with UV and one-dimensional intact cell matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (ICM MS) detection.