Raman in situ characterization refers monitoring the process using Raman spectroscopy without destroying the sample in real time, and then characterize the structure and performance change on site orrecord the real-time information throughout the process. Under operating conditions of the devices, examining the chemical and physical structure changes exactly in place where it occurs, will help to insight the relationship between microstructure and photoelectric properties of devices，and then optimize the structure to improve the performance. This review summarizes the in situ observation of film growth, degradation, charged state and their characteristics in organic optoelectronic devices, and finally makes a point on the applications and potentiality of in situ Raman spectroscopy in organic optoelectronic device.