Lithium iron pyrophosphate has drawn great attention because of its interesting physical and electrochemical properties, whereas its high rate capability is far from satisfactory. We synthesize nano-Li2FeP2O7/C with hierarchical pore via a low cost method which uses iron powder instead of Vitamin C as the reducing agent. The hierarchical pore is constructed through a “combustion” mechanism according to the thermogravimetric and morphological characterizations. The phase-pure nanoparticles of Li2FeP2O7 are embedded in the three-dimensional network of amorphous carbon. The hierarchical pore together with the two-dimensional diffusion channel of lithium in Li2FeP2O7 is beneficial to lithium diffusion capability which is evaluated by the lithium diffusion coefficients calculated from the results of GITT measurements. The fast lithium intercalation chemistry facilitates the reversible de/intercalation of lithium, resulting in the high cycling stability and rate-capability. After 100 cycles at the current density of 1C, 93.8% of the initial capacity is retained. The discharge capacity is 62.1 mAh g−1 at the current density of 4C. Therefore, the hierarchically porous nano-Li2FeP2O7/C is a promising cathode material for advanced rechargeable lithium ion battery.