This study examines the direct assembly of hybrid graphene nanosheets (GNSs) and multiwalled carbon nanotubes (MWCNTs) onto Ni current collectors in the presence of an electric field. The dissociation of Ni nitrate salt, which provides ions to charge the GNSs and MWCNTs positively, facilitates the homogeneous dispersion of each powder and assists in electrophoretic deposition. Direct assembly by this electrophoretic deposition results in the effective packing of GNS/MWCNT composites without any appreciable agglomeration, which is desirable for achieving high electrochemical performance of the composite electrodes in Li-ion batteries. Hence, GNS/MWCNT composite electrodes exhibit higher specific capacity compared to electrodes made of pure GNSs or MWCNTs owing to better realization of electrolyte permeability and Li-ion transfer.