Multiwalled carbon nanotubes (MWNTs) were functionalized by grafting Triton X-100 on their surface to improve their dispersion in a solution of polyacrylonitrile ( PAN) matrix. Well-aligned composite nanofibres containing PAN and MWNTs were prepared by electrospinning in dimethyl formamide solution, and a collector consisting of two pieces of electrode was used to catch the nanofibres, as well as a slowly rotating drum with multi-electrodes. The nanofibres, with diameters of similar to 100 nm, can be uniaxially aligned across the gap between the parallel electrodes. TEM images showed that the individual surface-functionalized MWNTs were embedded within the nanofibres.