A ZnO:Ga single crystal with an applicable size of φ40 × 1 mm was prepared using the hydro-thermal method. The crystal exhibits good crystallinity and scintillation properties with a 63.94-arcsec full-width at half-maximum (FWHM) in the X-ray rocking curve (XRC) spectrum, 8% luminous non-uniformity, emission at 389 nm in the X-ray excited luminescence spectrum, fast response and 5.5% BGO luminous intensity. Furthermore, an X-ray pinhole imaging system of nanosecond temporal resolution with a ZnO:Ga single-crystal image converter was established to diagnose the cathode electron emission spatial distribution of an intense current diode. Results for shutter times of 4 μs and 5 ns were obtained, which directly represent the cathode electron spatial distribution throughout the entire pulse duration and during a certain moment of the pulse, respectively. The results demonstrate that the large ZnO:Ga single crystal can diagnose the spatial distribution of cathode electron emission in an intense current diode with high temporal resolution and provide new solutions for high-temporal-resolution diagnosis of a pulse radiation field.