Highly activated Co/Mn-1,4,5,8-naphthalenetetracarboxylate (Co-NTC or Mn-NTC) was prepared from NTCDA, via a simple rheological phase method. This highly activated Co-NTC or Mn-NTC complex could spontaneously combust in air to yield nanosized metal oxide at ambient temperature. Discharge–charge cycling demonstrates that the combustion product (metal oxide) from Co-NTC or Mn-NTC (after heated at 400°C) as anodes for Li-ion batteries delivers high initial discharge and charge capacities, with excellent cycling stability.