The current study reports a kind of ternary deep eutectic solvent (DES) based on choline chloride, urea, and glycerol for the dispersion of multi‐walled carbon nanotubes (MWCNT) in the presence of surfactant. MWCNT‐embedded organic gels were subsequently prepared from the polymerization of resorcinol and formaldehyde in the obtained MWCNT‐dispersed DES. It has been demonstrated that the as‐prepared DES is excellent in dispersing and stabilizing the MWCNT, and thus allows the in situ synthesis of MWCNT functionalized resorcinol‐formaldehyde xerogels with no visible phase‐separation during the long sol‐gel process. After ambient drying and carbonization, MWCNTs can be well dispersed within the carbon xerogel matrix. The obtained carbon material possesses increased electrical conductivity while preserves the well‐developed porous structure. When used as electrodes in supercapacitors, it exhibits enhanced capacitance as well as rate performance. The specific capacitance at 0.5 A g−1 was 228 F g−1, 22 % more capacitance than that of the pristine carbon xerogel. More remarkably, it provides the electrodes with more than 200 % enhancement in capacitance when compared with that of the MWCNT‐embedded carbon xerogel prepared in aqueous solvent under the same conditions.