Surface modification of carbon nanotubes (CNTs) has been widely studied for some years. However, the asymmetric modification of individual CNTs with different molecular species/nanoparticles at the two end-tips or along the nanotube length is only a recent development. As far as we are aware, no attempt has so far been made to asymmetrically functionalize individual CNTs with moieties of opposite charges. In this paper, we have demonstrated a simple, but effective, asymmetric modification of the sidewall of CNTs with oppositely charged moieties by plasma treatment and pi-pi stacking interaction. The as-prepared asymmetrically sidewall-functionalized CNTs can be used as a platform for bottom-up self-assembly of complex structures or can be charge-selectively self-assembled onto and/or between electrodes with specific biases under an appropriate applied voltage for potential device applications.