The behaviour as the potential negative electrode in lithium-ion batteries of graphite-like materials that were prepared by high temperature treatment of unburned carbon concentrates from coal combustion fly ashes was investigated by galvanostatic cycling. Emphasis was placed on the relation between the structural/morphological and electrochemical characteristics of the materials. In addition, since good electrode capacity retention on cycling is an important requirement for the manufacturing of the lithium-ion batteries, the reversible capacity provided by the materials prepared on prolonged cycling (50 cycles) was studied and the results were compared with those of petroleum-based graphite which is commercialized as anodic material for lithium-ion batteries. The graphite-like materials prepared lead to battery reversible capacities up to ∼310mAhg−1 after 50 cycles, these values were similar to those of the reference graphite. Moreover, they showed a remarkable stable capacity along cycling and low irreversible capacity. Apparently, both the high degree of crystallinity and the irregular particle shape with no flakes appear to contribute to the good anodic performance in lithium-ion batteries of these materials, thus making feasible their utilization to this end.