Insulation materials with excellent dielectrics−vacuum interface breakdown strength are irreplaceable in equipment such as particle accelerators, fusion ignition, and related aerospace devices. In this article, the segment structure of a typical insulation polymer, polystyrene, has been modified by introducing divinylbenzene to form cross-linking junctures and adjust the cross-linking density. The influence of cross-linking on its electron absorb-emit feature and further on the vacuum pulsed flashover characteristics has been systematically studied. A series of broadband dielectric spectroscopy (BDS) and thermally stimulated current (TSC) experiments indicate that this cross-linking network inhibits the movement of the polar segments, leading to a drastic change in the charge-trapping behavior of dielectric surface layer materials. The trapping charge density is increased, and the trapping energy is transferred to deeper-level regions. These lead to the observed suppression of secondary electron emission (SEE) of highly cross-linked polystyrenes exposed in vacuum. And, quite sensibly, the nanosecond pulsed vacuum flashover tests show that the polystyrenes with higher crosslinking density have enhanced flashover strength. Moreover, to further investigate the relationship between the dielectric SEE behavior and its vacuum flashover process, a 2-D model is established and analyzed on the basis of the particle in the cell with the Monte Carlo collision (PIC-MCC) method.