In the last twenty years, the application of microreactors in chemical and biochemical industrial processes has increased significantly. The use of microreactor systems ensures efficient process intensification due to the excellent heat and mass transfer within the microchannels. Monitoring the concentrations in the microchannels is critical for a better understanding of the physical and chemical processes occurring in micromixers and microreactors. Therefore, there is a growing interest in performing in-line and on-line analyses of chemical and/or biochemical processes. This creates tremendous opportunities for the incorporation of spectroscopic detection techniques into production and processing lines in various industries. In this work, an overview of current applications of ultraviolet–visible, infrared, Raman spectroscopy, NMR, MALDI-TOF-MS, and ESI-MS for monitoring (bio)catalytic processes in continuously operated microreactor systems is presented. The manuscript includes a description of the advantages and disadvantages of the analytical methods listed, with particular emphasis on the chemometric methods used for spectroscopic data analysis.