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Spectroscopic and microscopic techniques are complementary to electrochemical studies because electrochemical data consists of current, voltage and time, and has no direct information concerning the chemical structure of active species. Hence electrochemical in situ/operando spectroscopy and microscopy become powerful tools for identification of the electrochemically active species during the electrochemical reactions. The present comprehensive paper provides the fundamental theory, cell design concepts, and measurement tips of various spectroscopic and microscopic techniques. X-ray absorption spectroscopy, infrared spectroscopy, surface plasmon resonance, Raman spectroscopy, confocal microscopy and electron microscopy are covered in the present paper. The introduced cell design becomes the critical part for chemists and materials scientists to start these measurements. Several advanced techniques from recent studies are also introduced.