In this investigation, the microstructural and dielectric properties of pure BaTiO3 and vanadium (V 5+ ) substituted on Ba 2+ site (A-site) and Ti 4+ site (B-site) in BaTiO3 ceramic have been studied. The three compositions of BaTiO3 (BT), Ba0.9V0.1TiO3 (BTA) and BaTi0.9V0.1O3 (BTB) were synthesized using solid-state reaction route. The XRD analysis of all three compositions has been carried out at room temperature and proper phase formation for BT, BTA and BTB are confirmed. However, compositions BTA and BTB indicate the presence of secondary phases, and it may be due to higher amount of vanadium substitution at A and B sites. Addition of vanadium inhibited the grain growth of BaTiO3 ceramic. Vanadium substitution on A- and B-site have resulted in decrease of Curie temperature as well as dielectric loss compared to pure BT. A more diffused behavior is observed in vanadium substituted samples as compare to pure BT which shows a sharp transition and lower value of diffuseness parameter. Impedance study shows that substitution of vanadium on A- as well as B-site results in decrease of AC conductivity. These properties of vanadium substituted samples can be utilized to reduce the dielectric loss in capacitors and in radio frequency applications.