With high portability and favorable performance, miniature mass spectrometers have become one of the most attractive tools for on-site analysis of trace volatile compounds. Based on the "Brick" mass spectrometer (BMS) developed previously, a hand-held BMS integrated with a photoionization source (PI-BMS) was developed in this study for volatile compound analysis. With compact dimensions of 30 cm × 18.5 cm × 27.6 cm (length × width × height), the PI-BMS was equipped with a 10.6 eV UV lamp and capable of generating molecular ions. The capabilities of qualitative and quantitative analyses for different volatile samples were demonstrated and characterized. Under optimized conditions, high detection sensitivity in open air was obtained for the PI-BMS with a limit of detection (LOD) of ∼10 ppbv. As demonstrations of mixture analysis, four different fresh fruits were directly analyzed using PI-BMS, observing characteristic mass spectra for each type of fruit.