Graphene-decorated LiFePO4 composite is synthesized for the first time through in-situ pyrolysis and catalytic graphitization, in which glucose and a trace amount of FeSO4 are employed as the graphene source and catalyst precursor, respectively. Under Ar/H2 (95:5) atmosphere at 750 °C, FeSO4 is thermally reduced to Fe nano-particles (Fe NPs) and glucose is pyrolyzed to carbon fragments first, followed by the in-situ growth of graphene sheets directly on the LiFePO4 nano-particles (LFP NPs) surface through the realignment of carbon fragments under the catalytic effect of the Fe NPs. The graphene sheets not only form a compact and uniform coating layer throughout the LFP NPs, but also stretch out and cross-link into a conducting network around the LFP particles. The LiFePO4@graphene composite displays a high reversible specific capacity of 167.7 mAh g−1 at 0.1C rate, superb rate performance with discharge capacity of 94.3 mAh g−1 at 100C rate and much prolonged cycle life. The remarkable electrochemical improvement is attributed to both electric and ionic conductivity increase as a result of in-situ grown graphene coatings along the LFP surface and the graphene network intrinsically connecting to the LFP particles.