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Carbon nanotubes (CNT) are amongst the most studied nano-materials for their application in numerous fields as a result of their exceptional mechanical, thermal, and electronic and optical properties. However, the lack of solubility of CNT in many common solvents limits the exploration of their potential applications. For this reason, it is important to investigate new procedures to functionalize these materials in order to improve their solubility and their processability. Furthermore, functionalization can modify the physical properties of CNT and thus expand their potential applications.We report herein the functionalization of single-wall carbon nanotubes (SWCNT) by cycloaddition reactions with arynes under microwave irradiation. The efficiency of the functionalization was monitored by XPS, FTIR and Raman spectroscopies, TGA and HR-TEM. All experimental results point to the formation of SWCNT with a high degree of functionalization, with mass increases ranging from 6.4% to 15.1% depending on the aryne substitution.