Atomic-scale precision alignment is a bottleneck in the fabrication of next-generation nanoelectronics. In this study, a redox-coupled inherently selective atomic layer deposition (ALD) is introduced to tackle this challenge. The 'reduction-adsorption-oxidation' ALD cycles are designed by adding an in-situ reduction step, effectively inhibiting nucleation on copper. As a result, tantalum oxide exhibits selective deposition on various oxides, with no observable growth on Cu. Furthermore, the self-aligned TaO x is successfully deposited on Cu/SiO 2 nanopatterns, avoiding excessive mushroom growth at the edges or the emergence of undesired nucleation defects within the Cu region. The film thickness on SiO 2 exceeds 5 nm with a selectivity of 100%, marking it as one of the highest reported to date. This method offers a streamlined and highly precise self-aligned manufacturing technique, which is advantageous for the future downscaling of integrated circuits.