In this paper, monodispersed LiFePO4 nanopillows have been successfully synthesized via solvothermal route with ethylene glycol (EG) as reaction medium. Subsequently, with the basis of the solvothermally synthesized monodispersed LiFePO4 nanopillows, monodispersed LiFePO4@C core–shell nanostructures are facilely prepared in high yield. Based on the experimental results, the formation mechanism of the monodispersed LiFePO4 nanopillows has been discussed simply. The monodispersed LiFePO4@C core–shell nanostructures exhibit nice capacity retention and high rate capacity due to the full carbon-coating and the well-crystallized nanosized particles.