We investigated the optical third harmonic generation (THG) signal from nanostructure-covered microcubes on Ni. We found that the hierarchical structures greatly change the third-order optical nonlinearity of the metallic surface. While the symmetry and lightning rod (LR) effects on microstructures did not significantly influence the THG, the localized surface plasmon (LSP) effect on the nanostructures enhanced it. By removing the nanostructures on the hierarchical structures, THG intensity could be strongly suppressed. In the present paper, we also discuss the mechanism that enhances THG in nano/micro structures.