Nanosurface patterning can be advantageous for novel opto-electrical devices application. In this study, we utilized the electron beam lithography (EBL) technique to fabricate ZnO nanorods(NRs)/ZnO/Si surface nanopatterning via galvanic submerged photo-synthesis of crystallites (G-SPSC) method, which combines galvanic reactions between two semiconducting surfaces and a photo-induced crystallization in water. By controlling the UV illumination time, high aspect ratio of ZnO NRs were precisely grown on 500 nm size of circular, linear, and lattice patterns. Using bromothymol blue (BTB) gel, a “photo-induced” galvanic reaction was visualized in G-SPSC. Room-temperature photoluminescence (PL) and cathodoluminescence (CL) results dictates oxygen vacancy (VO), ZnO/Si interface luminescence, as well as localized surface plasmon resonance (LSPR) phenomena on the ZnO NRs/ZnO/Si surface. Distinct luminescence behavior was illustrated by color-toned surface patterning (CTSP), opening a possibility for facile fabrication of miniaturized LED application in nanoscale surface area.