The mechanistic description of gas sensing on inorganic, organic, and polymeric materials is of great scientific and technological interest. The understanding of surface and bulk reactions responsible for gas-sensing effects will lead to increased selectivity and sensitivity in the chemical determination of gases and thus to the development of better sensors. In recent years, spectroscopic tools have been developed to follow the physicochemical processes taking place in an active sensing element in real time and under operating conditions. Thus, the monitoring of the processes in "living" gas sensors is no longer an unsolvable problem. This Review gives an overview of in situ and operando spectroscopic techniques for the study of gas-sensing mechanisms on solid-state sensors.