The concentration of nitrate in aquatic systems is rising with the development of modern industry and agriculture, causing a cascade of environmental problems. Here we describe a previously unreported nitrate formation process. Both indoor and outdoor experiments are conducted to demonstrate that nitrate may be formed from abundant atmospheric nitrogen and oxygen on nano-sized titanium dioxide surfaces under UV or sunlight irradiation. We suggest that nitric oxide is an intermediate product in this process, and elucidate its formation mechanisms using first-principles density functional theory calculations. Given the expanding use of titanium dioxide worldwide, such a titanium dioxide-mediated photocatalysis process may reveal a potentially underestimated source of nitrate in the environment, which on one hand may lead to an increasing environmental pollution concern, and on the other hand may provide an alternative, gentle and cost-effective method for nitrate production.