In this work, a simple, facile growth approach for a vertically aligned ZnO thin film is fabricated and its application towards methane gas sensors is demonstrated. ZnO thin film was prepared by a combination of hydrothermal and sputtering methods. First, a ZnO seed layer was prepared on the substrate through a sputtering technique, then a ZnO nanorod was fabricated using a hydrothermal method. The surface morphology of the ZnO film was observed by scanning electron microscopy (SEM). A ZnO nanorod coated on the dense seed layer is clearly visible in the SEM image. The average size of the hexagonal-shaped ZnO rod was around 50 nm in diameter, with a thickness of about 1 mm. X-ray absorption near-edge structures (XANES) were recorded to characterize the structural properties of the prepared film. The obtained normalized Zn K-edge XANES of the film showed the characteristic features of ZnO, which agreed well with the standard ZnO sample. The measurement of Zn K-edge XANES was performed simultaneously with the sensing response. The results showed a good correlation between sensor response and ZnO structure under optimal conditions.