The orbital binding energy and Fermi level of individual element of amorphous and crystallized Zr55Cu30Al10Ni5 alloys were measured by XPS. The relationship between the electron structure and the capability of field emission of the alloys was investigated. The breakdown strength in vacuum of the amorphous and thereafter crystallized alloys were investigated. It is found that Zr-based bulk amorphous alloys have greater work function than the crystallized alloys. Comparing with the crystalline Zr55Cu30Al10Ni5 alloy with a more centralized distribution, the dielectric strengths of amorphous Zr55Cu30Al10Ni5 alloy are more disperse. It can be concluded that Zr-based bulk amorphous alloys have higher dielectric strength than the crystallized alloys.