Functionalization of carbon nanotubes is essential for achieving their mechanical, electrical, and biological functions and enhancing their dispersion in a polymer matrix. Cycloaddition reactions can play a significant role as an emerging route in this direction. This minireview focuses on covalent functionalization of carbon nanotubes using a facile approach via a Cu(I)-catalyzed Huisgen [3+2] cycloaddition reaction. Through this reaction, an enormous variety of molecules can be coupled onto carbon nanotubes in a very controlled manner, and may be utilized for many potential applications from nanoelectronics to bio-applications.