With the development of vacuum electronic devices toward high power, high frequency, and miniaturization, the voltage holdoff capacity of the insulation materials in devices has also been raised to a higher demand. Cr/Mn/Ti-doped Al2O3 ceramics were prepared, and the bulk density, micromorphology, phase composition, resistivity, secondary electron emission coefficient, and surface flashover threshold in the vacuum of the Al2O3 were characterized. The results show that the addition of TiO2 to the Al2O3 ceramic can promote the sintering of the ceramic. The Cr/Mn/Ti-doped Al2O3 ceramic with a homogeneous microstructure can be obtained by an appropriate amount of TiO2 addition. In the process of the heat treatment, the TiO2 in the ceramics was reduced to a certain degree, which had an impact on the microstructure of the Al2O3 ceramic. Adding a small amount of TiO2 can improve the voltage holdoff performance in the vacuum. The value of the surface flashover threshold in the vacuum of the Cr/Mn/Ti-doped Al2O3 ceramic containing 1 wt.% TiO2 reached a value of 33 kV, which is 32% higher than that of the basic Al2O3 ceramic. The preparation of Al2O3 ceramics with a high voltage holdoff capacity in a vacuum provides fundamental technical support for the development of vacuum electronic devices.