The electrochemical performance of LiCoPO4-based electrodes was studied in dependence on synthetic conditions. The role of particle size distribution is illustrated. Structural changes occurring at lithium extraction–insertion were explored by ex situ and in situ synchrotron XRD measurements. For the samples annealed at temperature lower than 600°C the amorphisation of the cathode material was identified. For a high-temperature sample the two-phase character of electrochemical reaction was confirmed. The character of structural changes observed at charge and discharge is different: the two-phase reaction LiCoPO4–“CoPO4” occurs during charging, while discharge induces a strong increase of the cell volume for the Li-poor phase.