Self-activated phosphor Ba₂V₂O₇ microrods were prepared by the hydrothermal reaction method. Structural refinement was conducted on the basis of the X-ray diffraction (XRD) measurements. The morphological properties of the sample were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The chemical elements of the microrods were determined by energy dispersive spectrometry (EDS) measurements. The Ba₂V₂O₇ microrods have a big length–diameter ratio with a diameter of 10–50 μm and length of 0.5–2 μm. The UV-vis optical absorption of the Ba₂V₂O₇ microrods shows a direct allowed electronic transition with a band energy of 3.22 eV. The photoluminescence properties were studied such as emission and excitation spectra, the decay curve and lifetime, color coordinates and the absolute internal quantum efficiency (η). Notably, the Ba₂V₂O₇ microrods present bright luminescence with a high quantum efficiency of 47.5%. It is suggested that Ba₂V₂O₇ microrods could be used for efficient lighting and displays. Moreover, Ba₂V₂O₇ microrods show scintillating properties, which were confirmed by X-ray excited luminescence (XEL) at room temperature. The morphological characteristics of the microrods could also have the potential to greatly reduce the cost of fabricating flexible lighting devices.