In this study, the electronic structures of Fe- and/or V-doped rutile TiO₂ have been investigated using the first-principles calculations based on the density functional theory. Theoretical results show that the band gap of pure rutile is 1.98 eV. The top of the valence band is mainly formed by O2p and Ti3d states, in which O2p state plays a major role, while the conduction band is dominated by Ti3d state. In the calculations of doped models, a 2×2×2 super-cell structure (Ti₁₆O₃₂) is built based on the optimized geometric parameters of rutile. One Ti atom is replaced by a Fe or V atom with a doping amount of 6.25%. Fe and V are used to substitute the two nearest-neighbor Ti atoms parallel to the c-axis respectively so as to form the co-doped rutile with a doping quantity of 12.5%. The results show that Fe-doped rutile TiO₂ has a band gap of 2.18 eV, and the hybridization of Fe3d and O2p orbital introduce two intermediate bands in the middle of the forbidden band. The band gap of V-doped rutile is reduced to 1.80 eV and the intermediate state right below the bottom of the conduction band is attributed to the hybridization of V3d and O2p orbital, which acts as a shallow donor level. Fe- and V-codoping reduces the band gap of rutile to 1.73 eV and introduces a wide intermediate band into the forbidden gap. The emergence of the intermediate state and the decrease of the band gap make Fe- and V-codoped rutile possess a better responding capability to visible light. Meanwhile, isomorphous substitution of Fe or V atoms for Ti causes significant distortion to MO₆ octahedra, which could increase the concentration of surface defects, and thereby provide active sites for photocatalysis. These results supply theoretical aids to profound understanding of the photocatalytic mechanism of Fe- and V-bearing natural rutile under visible light.