Low-voltage rechargeable microbatteries having a vanadium-based cathode are provided. In one aspect, a method of forming a battery is provided. The method includes the steps of: forming a first contact on a substrate; forming a cathode on the first contact, wherein the cathode is formed from a vanadium-containing material; forming a solid electrolyte on the cathode; forming an anode on the solid electrolyte; and forming a second contact on the anode. A battery having a vanadium-based cathode is also provided.