The invention relates to a photo ionization mass spectrum imaging device combing with desorption electrospray ionization, comprising a mass spectrometer and a desorption electrospray ionization mechanism; the improvement lies in that a photo ionization mechanism is additionally arranged, and comprises a changeover mechanism and a light source mechanism; the light source mechanism is a synchronousradiation light and laser photo ionization mechanism or a vacuum ultraviolet light source mechanism. In detection and analysis, a solvent flows out from the desorption electrospray ionization mechanism to be used for desorbing a compound in a biological tissue on a glass slide, and the desorbed compound enters the photo ionization mechanism, is ionized by synchronous radiation light and laser or vacuum ultraviolet light, and enters mass spectrum to be analyzed and imaged. According to the invention, mass spectrum information is combined with movement of a two-dimensional sample moving platformto realize synchronous imaging of polar and non-polar compounds in the biological tissue, and in combination with the advantage of photo ionization, the device has wide prospects in the aspects of physiological disease, tumor research and the like in the future.