The exchange of lithium for univalent copper in CuNbO3 has been investigated. A new form of LiNbO3 with a lamellar structure has been synthesized from the topotactic reaction between CuNbO3 and a molten salt corresponding to the eutectic “LiCl/LiNO3”. This compound crystallizes in the P21/a space group with a = 9.433 Å, b = 8.226 Å, c = 6.213 Å, and β = 90.2°. This new phase intercalates one lithium on the first discharge and shows reversibility of 0.7 lithium through a first-order transformation leading to a capacity of 120 mAh/g at a potential of 1.65 V vs Li+/Li. © 2011 American Chemical Society.