A compound of bismuth coated with carbon is synthesized via a facile reduction using a kind of organic framework based on bismuth ligands metal as a precursor, with an average nanospheres diameter about 29 nm. The arrival of the carbon matrix not only alleviates the volume expansion of Bi nanoparticles upon Li insertion/extraction process but also supplies a highly electronic conducive to accelerate the lithiation/delithiation of the Bi electrode. When used as an anode material for lithium-ion battery, the Bi/C verifies an admirable reversible capacity of 1312 mAh g−1 for initial cycle and superb cyclability with a capacity of 515 mAh g−1 after 150 cycles. In view of these contributions, it can be concluded that the Bi/C acquired by a new approach is expected to be a potential anode material for sustainable development of LIBs.