Multicomponent and multifunctional hybrid structures based on microsized carbon fibers sheathed with aligned carbon nanotubes and their derivatives have been successfully prepared, and have been demonstrated to be an effective means for connecting nanoscale entities to the outside world and to possess interesting electrochemical properties attractive for a wide range of potential applications, including in methanol direct fuel cells and highly sensitive biological and chemical sensors. Judicious modification of the carbon-fiber-supported aligned carbon nanotubes with various functional moieties could lead to a class of novel multidimensional, multicomponent, and multifunctional materials of practical significance.