We report on the synthesis and surface characterization of thin-film nanocomposites using functionalized single-walled carbon nanotubes (CNTs) with a diamine-terminated oligomeric poly(ethylene glycol) [poly(ethylene glycol) bis (3-aminopropyl)-terminated 1500]. The functionalized CNT samples are soluble in highly polar solvents. Their common solubility allows for the intimate mixing of the functionalized nanotubes with the matrix polymer–poly(vinyl alcohol) by dip coating and wet casting to form nanocomposite thin films. We demonstrate the alignment of the CNT bundles in the thin films that are formed without the external field forces. We present our results and discuss alignment reorientations from the characterizations of the nanocomposite thin films by using a Raman spectrometer, scanning electron microscopy, and atomic force microscopy.