Hierarchically-aligned single-walled carbon nanotube (SWNT) films over large areas were fabricated by using Langmuir-Blodgett (LB) technique. Thiophenyl-modified SWNTs spreading solution in chloroform was prepared through amidation reaction of oxidized SWNTs. The resulting SWNTs were found to form stable colloidal suspensions in organic solvents, such as chloroform, which is a suitable solvent for the LB application. The compression of the thiophenyl-modified SWNTs spread onto the water surface of an LB trough leading to a uniform SWNT Langmuir monolayer, where SWNTs were aligned parallel to the trough barrier. Optical anisotropy of SWNTs LB films on quartz substrate was confirmed by polarized UV-Vis/NIR spectroscopic measurement. Moreover, the electrical conductivity of the resulting SWNT films, which were parallel to the tube axis, was found to be approximately 15 times higher than those that were perpendicular to the axis, reflecting anisotropic electrical properties due to the uniaxial alignment of individual SWNT bundles.