Structural, morphological and electrochemical characterizations in EC:DMC-LiPF6 of carbon-coated LiMnPO4 and LiMn1−x Fe x PO4 (x = 0.2, 0.3) cathode materials synthesized via a cost-effective procedure based on sol–gel (from partially or totally soluble precursors in water), pyrolysis and ball milling steps are reported. Carbon-coated LiMnPO4 obtained from totally soluble precursors featuring at 0.1 C 125mAhg−1 at 50 °C and 95mAhg−1 at 30 °C, with a capacity fade per cycle of 0.5% at 50 °C and 0.4% at 30 °C, is a very promising material, particularly in consideration of the inexpensive procedure that was pursued for its synthesis.