To improve the practical application of carbon nanotubes, it is critically important to extend their physical properties from the nanoscale to the macroscopic scale. Recently, chemists aligned continuous multiwalled carbon nanotube (MWCNT) sheets and fibers to produce materials with high mechanical strength and electrical conductivity. This provided an important clue to the use of MWCNTs at macroscopic scale. Researchers have made multiple efforts to optimize this aligned structure and improve the properties of MWCNT sheets and fibers. In this Account, we briefly highlight the new synthetic methods and promising applications of aligned MWCNTs for organic optoelectronic materials and devices. We describe several general methods to prepare both horizontally and perpendicularly aligned MWCNT/polymer composite films, through an easy solution or melting process. The composite films exhibit the combined properties of being flexible, transparent, and electrically conductive. These advances may pave the way to new flexible substrates for organic solar cells, sensing devices, and other related applications. Similarly, we discuss the synthesis of aligned MWCNT/polymer composite fibers with interesting mechanical and electrical properties. Through these methods, we can incorporate a wide variety of soluble or fusible polymers for such composite films and fibers. In addition, we can later introduce functional polymers with conjugated backbones or side chains to improve the properties of these composite materials. In particular, cooperative interactions between aligned MWCNTs and polymers can produce novel properties that do not occur individually. Common examples of this are two types of responsive polymers, photodeformable azobenzene-containing liquid crystalline polymer and chromatic polydiacetylene. Aligning the structure of MWCNTs induces the orientation of azobenzene-containing mesogens, and produces photodeformable polymer elastomers. This strategy also solves the long-standing problems from the traditional mechanical rubbing method, which include production of broken debris and structure damage during fabrication and building up electrostatic charge during use. Aligning MWCNTs induces a conformational change in polydiacetylene, which causes the composite fibers to be electrochromatic, a previously unknown reaction in chromatic polymers. Due to their large surface area, flexibility, electrical conductivity, and remarkable electrocatalytic activity, aligned MWCNT films can be used as counter electrodes to produce highly efficient dye-sensitized solar cells. In addition, chemists have developed new electrodes from the aligned MWCNT fibers to make a family of high-performing, wire-shaped dye-sensitized solar cells.