The invention relates to the analysis technology field and especially relates to a method for analyzing a content of an imidacloprid synthetic intermediate through liquid chromatography-mass spectrometry. In the invention, a perfluorinated organic acid is taken as an ion-pairing agent. Under an ion-pairing chromatography condition, all the above intermediates can reach baseline separation and realize quantitative detection. Simultaneously, the ion-pairing agent is compatible with a mass spectrometry system and can be used for completing efficient separation and qualitative and quantitative detection in a liquid chromatography-mass spectrometry (LC/MS) system.