Single-crystalline Zn2SnO4 nanowires were successfully synthesized on a photoresist-coated Si substrate using a facile chemical vapor deposition method. The growth of the nanowires followed a self-catalytic vapor-liquid-solid process. During annealing, the photoresist was carbonized into a complex glassy and graphite carbon structure. The immiscibility between the carbon layer and the in-situ formed Zn2SnO4 was a prime factor in the formation of the one-dimensional Zn2SnO4 nanowires. A broad blue-red emission band centered at 490.4 nm was observed in the photoluminescence spectrum of these nanowires, and it was related to the oxygen vacancies in these nanowires.