A scalable and solvent‐free chemical process to obtain highly functionalized and dispersible multi‐walled carbon nanotubes is reported. Highly functionalized multi‐walled carbon nanotubes have been prepared using in situ generated aryl diazonium salts in the presence of ammonium persulfate and 2,2′‐azoisobutyronitrile by solvent‐free techniques. In the Raman spectra of the resulting materials, characteristic peaks, the D‐ and G‐bands, are shifted by about 10 cm?1 to lower frequencies. At the same time, the relative intensity ratios between the D‐ and G‐bands increase in comparison to that in the spectrum of the purified product. Fourier‐transform infrared spectroscopy reveals the presence of the functional groups on the surface. Transmission electron microscopy images directly confirm the significant build‐up of sidewall organic moieties on the treated materials. The weight loss of various functional moieties determined by thermogravimetry–differential scanning calorimetry analysis is about 18–33%. The dispersibility of the functionalized materials in solvents, such as chloroform, tetrahydrofuran, and water, is obviously improved.