Nasicon-type Li 3 Fe 2−2x Ti x Mn x (PO 4 ) 3 (x=0–0.2) cathodes were synthesized by a solid-state reaction route. The prepared powders were mixed with acetylene carbon using planetary milling to optimize the electrochemical performance. The galvanostatic charge/discharge test and the cyclic voltammetry (CV) indicated that both Li 3 Fe 2 (PO 4 ) 3 /C and Li 3 Fe 1.8 Ti 0.1 Mn 0.1 (PO 4 ) 3 /C cathodes showed two reversible redox phenomena at 2.8 and 2.7V for Fe 3+ /Fe 2+ couple versus Li/Li + upon discharge. The plateau potential of Ti 4+ /Ti 3+ versus Li/Li + at 2.5V is not observed because of the low content of Ti and the disturbance of Fe 3+ /Fe 2+ . In contrast, the plateau potential of Mn 3+ /Mn 2+ versus Li/Li + at 3.5V is observed. In addition, the Li 3 Fe 1.8 Ti 0.1 Mn 0.1 (PO 4 ) 3 /C cathode possessed higher reversibility and better capacity retention (122.3mAhg −1 at C/20 in the first cycle, approaching the theoretical capacity of 128mAhg −1 , and close to 90.8mAhg −1 at C/2 in the 20th cycle) than that of Li 3 Fe 2 (PO 4 ) 3 /C cathode.