Three dimensional graphenes (3DG) have been studied with the aim of examining their properties in lithium batteries. They were prepared through a hydrothermal exfoliation of graphitic oxide (GO), combined with a chemical reducing agent and a surfactant for controlling the restacking of the graphene sheets and the self-assembling sheets. The changes in the synthesis conditions led to variations in the structural, morphological, textural and oxygen-based functional groups, as revealed by the XRD-RS, SEM, N2 adsorption and XPS data, respectively. As electrodes for Li-ion batteries, they varied in their behavior, but had a common feature: high irreversible capacity values and strong polarization between the discharge and charge curve, typical of disordered carbons. The 3DG synthesized by simple hydrothermal treatment of GO and the GO itself delivered high discharge capacity values (higher than the graphite’s, 370mAhg−1), but the capacity retention along cycling was poor. 3DG is obtained with a mixed synthesis (hydrothermal treatment, sucrose as chemical reducing agent and sodium dodecyl sulfate as surfactant), which provided lower capacities, though the capacity retention on cycling was better. Among the different properties measured, only the oxygen-based functional groups showed a direct relationship with the electrochemical response observed. The bigger the oxygen content, the higher was the delivered discharge capacity, with a disappointing capacity retention on cycling as detrimental effect.