Ag@LiFePO4 cathode materials have been prepared successfully by performing solid-state reactions between AgNO3 and the ascorbic acid in the presence of LiFePO4 powders at ambient temperature. Metallic Ag nanoparticles of ca. 10 nm in diameter can be produced with the environmental benign approach and efficiently attached onto the surfaces of commercial LiFePO4 cathode materials. The as-prepared composites show highly enhanced electrochemical performances in storing Li with ca. 22% increase in their discharge specific capacity from 128 to 156 mAhg−1 at C/10 rate, after loading Ag additive of 2 wt%. The coulombic efficiency of the composites can retain 97%, after cycling for 80 times. They can also remain up to 94 mAhg−1 of their discharge specific capacity at high rate of 5 C, which is almost twice higher than that of LiFePO4 cathode materials.