The invention discloses an in-situ electrochemical infrared spectroscopic-mass spectrometric detection system and method. The system is composed of a three-electrode electrolytic bath, a surface-enhanced infrared reflectance spectroscopic analysis apparatus, an in-situ mass spectrometer and an in-situ infrared transmission spectroscopic analysis apparatus, wherein the three-electrode electrolytic bath is composed of a counter electrode electrolytic bath, a working electrode electrolytic bath, a reference electrode electrolytic bath and an ion exchange membrane; the surface-enhanced infrared reflectance spectroscopic analysis apparatus is composed of an attenuated total reflection infrared ray emitter, a ZnSe prism and a reflected infrared signal receiver; the in-situ mass spectrometer is composed of a mass spectrometric rod, a vacuum pump, a glass capillary and a PTFE membrane; and the in-situ infrared transmission spectroscopic analysis apparatus is composed of an electrolyte storage tank, a waste electrolyte tank, a peristaltic pump, a CaF2 capillary glass tube, an infrared transmission light emitter and an infrared transmission light receiver. The system and method provided have the advantages of complete and accurate test information, high sensitivity, a wide application scope, capacity of realizing arbitrary combination, easiness in manufacturing, etc.