In this study, a series of undoped and V₂O₅-doped SnO₂nanofibers were synthesized via the electrospinning technique. The morphological and microstructural properties of these nanofibers have been characterized by XRD (X-ray diffraction), FESEM (field emission scanning electron microscopy), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The gas sensing properties of the undoped and V₂O₅-doped SnO₂(V₂O₅/SnO₂= 0.5 mol%, 1 mol%, 2.5 mol% and 5 mol%) samples were tested for various gases. The sensor based on the S2 sample (V₂O₅/SnO₂= 1 mol%) exhibits the largest response toward 25 ppm benzene among these undoped and doped SnO2 nanofibers, exhibiting a response of about 6.25 to 25 ppm benzene, which is almost 3.2 times higher than that of the sensor based on pure SnO₂nanofibers at the optimum operating temperature. The response and recovery time to achieve 25 ppm benzene were about 3 s and 40 s, respectively. These results indicate that the benzene sensors based on the S2 sample exhibit high response, good repeatability and quick response-recovery kinetics.