The platelike Co3O4/carbon nanofiber (CNF) composite materials were synthesized by the calcination of β-Co(OH)2/CNF precursor prepared by a surfactant-free hydrothermal method. As negative electrode materials for lithium-ion batteries, the platelike Co3O4/CNF composites can deliver a high reversible capacity of 900 mAh g-1 for a life extending over hundreds of cycles at a current density of 100 mA g-1. The high Li-storage capacity and excellent cycling performance for Co3O4/CNF composite materials may mainly attribute to the beneficial effect of the CNFs addition on enhancing structural stability and electrical conductivity of Co3O4 platelets.