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)2m phases were measured and a relation with the amount of lithium inserted and m was also found.