The invention relates to a mass spectrometer analysis instrument, in particular to an atmospheric pressure photoionization source device for detecting volatile organic compounds in water. It includes two parts: a dynamic purging and bubbling device and an atmospheric pressure photoionization source. The dynamic purging and bubbling device mainly includes a glass vial, four capillaries, the outlet of the bubbling bottle, and a constant temperature water bath. Atmospheric pressure photoionization source includes ionization source cavity, vacuum ultraviolet lamp, repelling electrode, focusing electrode, transmission electrode, mass spectrometry sampling metal capillary, reagent gas inlet, high humidity sample inlet and make-up gas inlet. All the high-humidity sample gas purged from the bubble bottle enters the atmospheric pressure photoionization source. The invention improves the stability of detection, and the matrix in water has little influence on sample detection; the absorption of photons by neutral molecules and the consumption of reagent ions are reduced; the introduction of reagent gas can greatly improve the ionization efficiency. The designed atmospheric pressure photoionization source can realize rapid and highly sensitive detection of high-humidity samples.