Noncovalent functionalization approach was used to make negatively charged carbon nanotubes (CNTs) suspension in water medium. Stable alumina/CNT sol solution was consequently formed by simple titration process, which allowed high dispersibility of CNTs in final composite powders and final CNT/alumina (CA) nanocomposites. Moreover, these CA composite powders were transformed to continuous composite fibers via electrospinning technique. Very significant shear stresses exerted on alumina were well recorded and reflected by shifts of X-ray diffraction peaks. The as-fabricated CA fibers possess a specific surface area 30 times larger than that of pure poly(acrylic acid) fibers. The axial alignment of CNTs observed in the composite fibers is promising for developing textured ceramics, and also for the study of the effect of orientation of fillers on the mechanical and functional properties.