Abstract: Miniature VUV lamp is suitable for ionization source for portable mass spectrometer due to its small size and low power-consumption. However, the sensitivity based on VUV lamp is limited by low brightness and poor ion utilization in irradiation area. A radio-frequency enhancement single photoionization/chemical ionization (RF-SPI/CI) source based on VUV lamp was developed, which could increase detection sensitivity by improving ion transmission and chemical ionization methods. The sensitivity of radio-frequency enhancement ion source was 26 folds as high as that of single photoionization. The limit of detection (LOD) of benzene, toluene and p-xylene were 52, 53, 71 ng/m³, respectively. The RF-SPI/CI source has the advantages of small size and high sensitivity, which is suitable for portable mass spectrometer.