Constant-current anodization of pure aluminum was carried out in non-corrosive capacitor working electrolytes to study the formation mechanism of nanopores in the anodic oxide films. Through comparative experiments, nanopores are found in the anodic films formed in the electrolytes after high-temperature storage (HTS) at 130 °C for 240 h. A comparison of the voltage-time curves suggests that the formation of nanopores results from the decrease in formation efficiency of anodic oxide films rather than the corrosion of the electrolytes. FT-IR and UV spectra analysis shows that carboxylate and ethylene glycol in electrolytes can easily react by esterification at high temperatures. Combining the electronic current theory and oxygen bubble mold effect, the change in electrolyte composition could increase the electronic current in the anodizing process. The electronic current decreases the formation efficiency of anodic oxide films, and oxygen bubbles accompanying electronic current lead to the formation of nanopores in the dense films. The continuous electronic current and oxygen bubbles are the prerequisites for the formation of porous anodic oxides rather than the traditional field-assisted dissolution model.