Dielectric breakdown is the process of local materials transiting from insulating to conductive when the dielectric is submerged in a high external electric field environment. We show that the atomistic changes of the chemical bonding in a nanoscale breakdown path are extensive and irreversible. Oxygen atoms in dielectric SiO2 are washed out with substoichiometric silicon oxide (SiOx with x<2) formation, and local energy gap lowering with intermediate bonding state of silicon atoms (Si1+, Si2+, and Si3+) in the percolation leakage path. Oxygen deficiency within the breakdown path is estimated to be as high as 50%–60%.