Olivine type multi-walled carbon nanotube encrusted LiFePO4/C composites have been prepared using economic and energy efficient simple polyol technique without any subsequent heat treatment. The prepared material has an olivine type orthorhombic phase. Also, the iron oxidation state is 2+, which is identified by X-ray diffraction and X-ray photoelectron spectroscopy. It is possible to attain the discharge capacity almost close to theoretical capacity of LiFePO4 as in high temperature methods with ∼100% coulombic efficiency. The specific surface area has been increased upon encrusting multi walled carbon nano tube on LiFePO4/C, which results in enhanced reversible capacity upto 166 mAh g−1 at C/10. Also, it exhibits 89 mAh g−1 even at 30 C rate. This is due to the formation of conductive networks by carbon nanotube, and excellent attachment of LiFePO4/C composite particles on multi-walled carbon nanotube, which induced the kinetics during intercalation/deintercalation process. Multi-walled carbon nanotube acts as the electro-conductive filler on the LiFePO4 surface. The direct addition of MWCNT would result better performances than blending the MWCNT with LiFePO4/C.