Sol gel chemistry has been a useful technique to achieve hard-to-prepare metastable materials. Niobium oxide, for instance has a thermodynamic preference to crystallize on monocyclic lattice. Here, we were able to achieve synthesis of orthorhombic motif with a careful sol-gel preparation and tailored thermal treatment. Furthermore, formation of lithium inserted Nb205 phases were studied by electrochemical methods. When lithium is inserted, several single phases LixNb205 were observed in the range of 0 ≤ x ≤ 3.3 between 3.0 and 0.75 V. Even though the reaction is only reversible for x ≤ 1.8. Also, T-Nb205 polymorph showed improved intercalation characteristics.