High specific capacitance anode aluminum foils fabricated by introducing TiO2 to improve the permittivity (εr) of Al2O3 is one of the most effective ways to reduce the size and weight of aluminum electrolytic capacitors (AECs). However, the underlying mechanism by which the introduction of TiO2 causes capacity enhancement remains unclear. Here, a proposition is claimed that TiO2 is not directly responsible for the capacity enhancement but Al-doping TiO2 (AOT) actually. An atomically doping strategy based on atomic thermal diffusion and ionic electromigration is proposed to realize the fabrication of AOT via modulating the thermal and electric fields. Results show that the doping behavior of Al3+ induces the displacement of neighboring Ti4+ ions, which enhances the dipole polarization resulting in an increase of εr (25). Meanwhile, the diffusion of O2 and migration of O2– effectively removes the oxygen vacancy, enhancing the breakdown field strength (> 6 MV·cm−1) of dielectrics. Ultimately, the specific capacitance of anode foils is increased by about 50 % compared to those without AOT. On a brighter note, this work deepens the understanding of the capacity enhancement mechanism and will contribute to further facilitating the miniaturization of AECs.