Monoclinic NaV3O8 was prepared via aqueous precipitation and subsequently chemically lithiated using butyllithium in hexane as lithiation reagent. The topochemical lithiation process leads to materials with variable Lithium content depending on the lithiation reaction conditions. Up to 3 Li+ mol(-1) could be inserted chemically in the lattice water-free NaV3O8 and result in cleavage of the particles, which leads to highly dispersed materials. In contrast to the chemical insertion method, almost 3.5 Li+ mol(-1) could be electrochemically inserted in NaV3O8, corresponding to a specific charge of about 310 mAh g(-1). About 2.5 Li+ mol(-1) could be deinserted potentiodynamically in the potential range from 1.5 to 4.0 V vs Li/Li+ from a chemically lithiated material with the composition Li3NaV3O8. This corresponds to a specific charge of about 215 mAh g(-1). In galvanostatic cycling experiments, a specific charge of more than 200 mAh g(-1) could be demonstrated for 100 cycles using this electrode material. The specific charges obtained are independent ol the applied specific current up to 50 mA g(-1) of the oxide. This behavior indicates that the sodium vanadate host material can support high lithium insertion and deinsertion rates, which make the chemically lithiated form an attractive candidate for lithium-containing positive electrode materials in high-power lithium-ion batteries.