The usage of direct current (DC) voltage has enormous potential for oil fields due to the effect of wettability alteration. However, the unclear mechanism of the wettability alteration has limited the application of this technology to oil fields. In this study, chemical and physical methods including contact angle tests, Fourier-transform infrared spectroscopy (FTIR) measurements, and atomic force microscope (AFM) experiments were combined to investigate the wettability alteration mechanism for tight sandstones subjected to DC voltage treatment. From the view of a chemical factor, FTIR results show that DC voltage decreases the number of Si-O-Si, C-O-C, C-O, and COOH groups, while it also increases the number of C═O and OH groups. The changes in molecular groups further improve the water-wetting property of tight sandstones. On the other hand, in a physical way, AFM results indicate that DC voltage improves the roughness of the rock surface. At the same time, the wetting state transfers from the Cassie-Baxter to the Wenzel. This increases the contact area of the solid-liquid interface. The augment of roughness and the transfer of the wetting state improve the water-wetting property of tight sandstones. By comparing the influences of both chemical and physical factors on wettability, it is concluded that although roughness indeed affects the wettability, chemical factors play a dominant role in determining the wettability. Achievements in this study can help researchers and engineers better understand the mechanism of wettability alteration and further accelerate the development of tight sandstones with DC voltage-related technology.