Through observation of the binding energy spectra of V-2p(S = 3/2) and C-1s, and ESR measurements, we suggest that the nucleation agent formed during heat-treatment of a mixture of V2O5 and melamine-formaldehyde resin (polymeric carbon) is the complex VO(graphene)(2). First, this complex enables the carbon structure to become more ordered and increases its d(002) value. Second, the VO displays electron-absorbing ability. Third, the content of the imperfect carbon structure is decreased. All of these effects result in increased capacity and improved cycling behaviour of lithium secondary batteries using such material as the anode.