The hollow spherical LaFeO3 perovskite materials were assembled successfully via a templating method and attached calcination treatment. Detailed studies of LaFeO3 perovskites were conducted with regard to their microstructures, morphologies, compositions, and chemical bonding states. The electrochemical performances of hollow spherical LaFeO3 as lithium-ion battery anodes were illustrated. The discharge capacity was 981 mAh g−1 after 200 cycles at the current density of 500 mA g−1, and 316 mAh g−1 could be preserved even after 1000 cycles. The unique perovskite and stable hollow spherical structure not only provide LaFeO3 with improved circulation stability and capacity retention, but also effectively shorten the transport distance of Li+, strengthen the reaction kinetics and expand the electrode/electrolyte interface. In this study, hollow spherical LaFeO3 perovskites were discovered to be reliable candidates for lithium-ion battery anodes.