LiMPO4 (M=Mn, Fe) and LiMn0.4Fe0.6PO4 thin-films have been fabricated by electrostatic spray deposition (ESD) combined with sol–gel method, in which P2O5 was used as a phosphorous resource in Li–M–P–O alcohol precursor solution. Analyses of LiMPO4 solid films using X-ray diffractometry (XRD) and scanning electron microscopy (SEM) demonstrated the formation of an olivine phase of space group Pmnb with nanocrystalline morphology. The prepared LiMPO4 films were evaluated electrochemically by cyclic-voltammetry and charge/discharge measurements. The results showed that thin-film electrode of LiMn0.4Fe0.6PO4 exhibited better electrochemical performance than that of pure LiFePO4 and LiMnPO4.