Multi-walled carbon nanotubes with rectangular or square cross-section are formed. The nanotubes are about 50-200 nm in width, and their walls are around 5-30 nm thick. It is very likely that the rectangular cross-section is shaped simultaneously when nanotubes are formed from catalyst Fe nanoparticles during chemical vapor deposition process, and the shape is stabilized by the bonding between adjoining graphene layers in the multi-walled structure.