Lithium trivanadate, , can be prepared in a finely dispersed form by dehydration of aqueous lithium vanadate gels. Two methods of dehydration, both easily adaptable to large‐scale production, are described in this work: freeze drying and spray drying. After heat‐treatment of the dried gels (xerogels) to remove loosely bound water they show a high capacity for lithium insertion, approaching four additional lithium per formula unit, and good reversibility as electrode materials for high energy density lithium cells. How the heat‐treatment temperature influences the crystal structure is demonstrated as well as the electrochemical properties of the vanadium oxide.