A direct approach for the synthesis and coating of advanced nanocomposite negative electrodes via a single-step process at low temperature is presented. Metal-oxide/PVdF nanocomposites are obtained in one step by electrospray pyrolysis of precursor solutions containing dissolved metal salts together with polyvinylidene fluoride (PVdF) as binder. In this way, small oxide nanoparticles are generated and dispersed in situ in the binder creating nanocomposite structures, while being coated at once as thin electrode layers on stainless steel coin cell cans. The intimate contact between the nanoparticles and the binder favours enhanced adhesion of the materials in the overall electrode structure and adequate electrochemical performances are obtained without any conductive additive. Three nanocomposite oxide/PVdF materials (i.e. SnO2, CoO and Fe2O3) are reported here as preliminary examples of negative electrodes. The results show that this approach is suitable, not only for the fabrication of nanocomposite electrodes for Li-ion batteries, but also for other novel applications.