The well-controlled material assembly and patterning on indium tin oxide (ITO) coating layer is of great importance for the practical fabrication of a functional device. Nonetheless, the conventional way to achieve this aim is still mainly based on the combination of photolithography with pattern transfer techniques (e.g., wet/dry etching, mu CP) due to the lack of one method that is able to directly afford site-selective ITO surface tailoring and subsequent templating for material assembly. Herein, we reported a novel, fast, and efficient photochemical reaction to accurately tailor the surface property of ITO with light-controlled site-selectivity, thus resulting in direct photoresist-free and etching/contact-free lithographic patterning of building blocks, e.g., ZnO, BaTiO3, CdS, lipid membrane, conductive polymers, colloids, and liquid crystals. The entire process reveals new interfacial chemistry suitable for inorganic metal oxide and its important versatile implications for low-cost fabrication of large-area flat and flexible optical/electronic/biorelated devices.