Improvement in the time-zero dielectric breakdown (TZDB) endurance of metal-oxide-semiconductor (MOS) capacitor with stacking structure of Al/HfO2/SiO2/Si is demonstrated in this work. The misalignment of the conduction paths between two stacking layers is believed to be effective to increase the breakdown field of the devices. Meanwhile, the resistance of the dielectric after breakdown for device with stacking structure would be less than that of without stacking structure due to a higher breakdown field and larger breakdown power. In addition, the role of interfacial layer (IL) in the control of the interface trap density (Dit) and device reliability is also analyzed. Device with a thicker IL introduces a higher breakdown field and also a lower Dit. High-resolution transmission electron microscopy (HRTEM) of the samples with different IL thicknesses is provided to confirm that IL is needed for good interfacial property.