In this work it is presented a review of the main results obtained during the electrochemical lithium insertion in the family of monophosphate tungsten bronzes (PO2)(4)(WO3)(2m) (2 <= m <= 10). This family of oxides is a good system in order to study the relation among the electrochemical processes observed in the course of lithium insertion and the changes of bronzes structures. By means of X-ray diffraction experiments, the nature of Li-x(PO2)(4)(WO3)(2m) phases has been elucidated and a correlation with the reversible/irreversible processes observed during the electrochemical insertion has been established. The electrical properties of the inserted Li-x(PO2)(4)(WO3)(2n) phases were measured and a relation with the amount of lithium inserted and m was also found. (c) 2008 Elsevier Ltd. All rights reserved.