The invention discloses an on-line volatile organic compound underway monitoring system and an analysis method. The on-line volatile organic compound underway monitoring system comprises an underway vehicle; an industrial personal computer, a sampling module electrically connected with the industrial personal computer, a detection module, a data acquisition module, a display module, a data analysis module, an equipment control module, a storage module, a transmission module and a GIS module are arranged in the underway vehicle; the sampling module comprises a sampling pipe, a sampler and a nitrogen cylinder, the sampling pipe is connected with the sampler, and the nitrogen cylinder is connected with the sampling pipe and the sampler; and the detection module comprises an extractor, a concentrator and a gas chromatograph-mass spectrometer, the extractor is connected with the concentrator, the concentrator is connected with the gas chromatograph-mass spectrometer, the gas chromatograph-mass spectrometer is electrically connected with the industrial personal computer, and the sampler is connected with the extractor. Low-temperature sampling is kept, real-time quantitative online detection is achieved, pollution portraits in the area are suggested through area navigation, and pollution tracing, peculiar smell tracing, accurate strike and fine management are facilitated.