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Tin phosphide (Sn₄P₃) nanoparticles with different sizes are synthesized via a facile solvothermal method at 180 °C for 10 h. The as-prepared Sn₄P₃ nanoparticles have an average size of about 15 nm. Meanwhile, their size could be easily controlled by the solvent ratio. The long cycle stability and rate performance of the as-obtained Sn₄P₃ nanoparticles have been tested as an anode material for lithium ion batteries for the first time. Electrochemical measurements show that the Sn₄P₃ nanoparticles with a smallest size give the best cycling and rate performances. They deliver a discharge capacity of 612 mAh g⁻¹ after 10 cycles and could still maintain 442 mAh g⁻¹ after 320 cycles at the current density of 100 mA g⁻¹ within voltage limit of 0.01–3.0 V. Even after 200 cycles at a current density of 200 mA g⁻¹, the specific capacity still could be remained at 315 mAh g⁻¹. The improved electrochemical performances …