Electrode materials with homogeneous distribution of boron were obtained by heating mixtures of nanosized carbon-coated lithium iron phosphate and BPO4 in 3-9% weight at 700 °C. The materials can be described as nanocomposites containing i) LiFePO4, possibly doped with a low amount of boron, ii) FePO4 and iii) an amorphous layer based on Li4P2O7-derived material that surrounds the phosphate particles. The thermal treatment with BPO4 also triggered changes in the carbon coating graphitic order. Galvanostatic and voltammetric studies in lithium half-cells showed smaller polarisation, higher capacity and better cycle life for the boron-doped composites. For instance, one of the solids, called B6-LiFePO4, provided close to 150 and 140 mAhg-1 (87% and 81% of theoretical capacity, respectively) under C/2.5 and C regimes after several cycles. Improved specific surface area, carbon graphitization, conductivity and lithium ion diffusivity in the boron-doped phospholivine network account for this excellent rate performance. The properties of an amorphous layer surrounding the phosphate particles also account for such higher performance.