The combination of reaction-oriented electrochemistry with species-focussed spectroscopy in spectroelectrochemistry (SEC) allows for a more complete analysis of single and multiple electron-transfer processes and redox reactions in general. Practical considerations and guidelines are provided in this tutorial review, and selected examples involving UV-VIS-NIR and IR absorption spectroscopy as well as electron paramagnetic resonance (EPR) are presented to illustrate the potential and the applicability of this technique.