This article reviews the recent development of optical nanofabrication with self-assemble manner based on the non-adiabatic chemical reaction. In the first part of this article, we propose a new polishing method that uses near-field etching based on a non-adiabatic process, with which we obtained ultra-flat silica surface that had a minimum roughness of 1.37 Å. We believe our technique can be applied not only to flat substrates but also to three-dimensional substrates that have convex or concave surfaces. In the second part, we demonstrate the selective photochemical etching of Si in a self-organized manner, which strongly depends on the distribution of the optical near-field. This dependence was described by the virtual exciton-phonon-polariton model. The photoluminescence (PL) spectra from the etched Si exhibited a blueshifted PL peak at 1.8 eV, corresponding to Si nanocrystals of 2.8 nm diameter. Since, both method are based on the photochemical reaction they are compatible with mass-production and can be applicable to other materials.