LiFePO4 composites were synthesized by aqueous ball milling and carbon thermal reduction from FePO4 center dot 2H(2)O through a rheological phase using acetic acid as dispersant. The rheological phase assisted method using acetic acid as dispersant improved the homogeneity of mixing raw materials. Li deficiency and solid-solution Mg dopant in the lattice of LiFePO4 was created through controlled off-stoichiometry Li/Fe ratio. Li deficiency, solid-solution Mg doping and uniform carbon layer decreased electron transfer and Li-ion diffusion resistance. The optimal LiFePO4 composite exhibited a high rate capability with 153 mA.h.g(-1) at 1 C and 111 mA.h.g(-1) at 20 C as well as a stable capacity retention with 99% for 100 cycles at 2 C and 98% for 200 cycles at 5 C. The rheological phase assisted method from FePO4 with acetic acid as dispersant is a promising route for production of high quality LiFePO4 materials at a reasonable cost. (C) 2015 Elsevier Ltd. All rights reserved.