Herein we report a facile and efficient solid state synthesis of carbon coated lithium iron phosphate (LiFePO4/C) cathode material achieved through the pyrolysis of polytetrafluoroethylene (PTFE). The current investigation is comparatively analyzed with the results of the composites of LiFePO4/C (LFP/C) synthesized using polystyrene-block-polybutadiene (PS-b-PBD), polyethyhylene (PE) and sucrose as carbon precursors. The optimized LFP/CPTFE composite is synthesized at 700 °C using 10 wt.% PTFE. The composite exhibits remarkable improvement in capacity, cyclability and rate capability compared to those of LFP/C synthesized using (PS-b-PBD), PE and sucrose. The specific discharge capacities as high as 166 mA h g−1 (theoretical capacity: 170 mA h g−1) at 0.2 C and 114 mA h g−1 at 10 C rates were achieved with LFP/CPTFE. In addition, the composite exhibits a long-term cycling stability with the capacity loss of only 11.4% after 1000 cycles. PTFE shifts the size distribution of the composite to nanometer scale (approximately 120 nm), however the addition of sucrose and other polymers do not have such an effect. According to TEM and XPS analysis, LFP/CPTFE particles are mostly coated with a few nanometers thick carbon layer forming a core–shell structure. Residual carbon does not contain fluorine.