This invention relates to the field of mass spectrometry, and more specifically to a vacuum ultraviolet photoionization and chemical ionization combined ion source, which consists of a vacuum ultraviolet light source and an ion source chamber. An ion acceleration electrode, an ion repulsion electrode, an ion extraction electrode, and a differential interface electrode positioned inside the ion source chamber are arranged along the exit direction of the vacuum ultraviolet light beam in sequence and spaced, coaxial, and parallel from each other. The ion acceleration electrode, the ion repulsion electrode, the ion extraction electrode, and the differential interface electrode are all plate structures with central through holes. The vacuum ultraviolet light beam passes through the central through holes of the electrodes along the axial direction. By utilizing a single vacuum ultraviolet light source, the ion source is feasible to switch between two ionization modes, vacuum ultraviolet photoionization (VUV PI) and chemical ionization (CI), under suitable ion source pressure, thus greatly expanding the range of detectable samples.