Carbon nanotubes, in different forms and architectures, have demonstrated good promise as electrode material for Li-ion batteries, owing to large surface area, shorter Li-conduction distance and high electrical conductivity. However, practical application of such Li-ion batteries demands higher volumetric capacity, which is otherwise low for most nanomaterials, used as electrodes. In order to address this urgent issue, we have developed a novel 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries. The unique 3D design of the electrode allowed much higher solid loading of active anode material, MWCNTs in this case and resulted in more amount of Li+ ion intake in comparison to those of conventional 2D Cu current collector. Though one such 3D anode was demonstrated to offer 50% higher capacity, compared to its 2D counterpart, its ability to deliver much higher capacity, by geometrical modification, is presented. Furthermore, deposition of amorphous Si (a-Si) layer on the 3D electrode (a-Si/MWCNTs hybrid structure) offered enhancement in electrochemical response. Correlation between electrochemical performances and structural properties of the 3D anodes highlights the possible charge transfer mechanism.