The invention discloses a solid-phase dehydration extraction-supercritical fluid chromatography-mass spectrometry online analysis system, which includes an online enrichment-removal-cleaning device and an online dehydration-desorption-dilution-chromatographic separation device, and the device includes a carbon dioxide pump , three chromatographic pumps, two six-way switching valves, autosampler, extraction column, mixer, chromatographic column, three-way connector, mass spectrometer detector, through online enrichment-removal-cleaning device and online dehydration- The combination of desorption-dilution-chromatographic separation device realizes the online combination of supercritical fluid chromatography technology and pretreatment technology, enabling supercritical fluid chromatography technology to directly analyze aqueous samples. The entire analysis process is automatically controlled, with good chromatographic performance, high accuracy and precision, and can be effectively applied to the rapid analysis and detection of trace organic compounds in complex aqueous samples or aqueous extracts.