A dendrimeric phenoxy-substituted cyclotetraphosphazene has been prepared for the non-covalent functionalization of multiwalled carbon nanotubes (MWCNTs). The synthesized cyclotetraphosphazene derivatives (2–4) and dendrimeric cyclotetraphosphazene (5) have been characterized by standard spectroscopic techniques. The functionalization of MWCNTs with compound 5 has been accomplished and the resulting MWCNT-5 hybrid has been characterized by 31P NMR, 1H NMR, Raman spectroscopy, X-ray diffraction (XRD), energy dispersive X-ray (EDX), fluorescence, thermal gravimetric analysis (TGA) and high-resolution transmission electron microscopy (HRTEM) techniques. The results showed that the dendrimeric compound 5 has been attached to the MWCNTs via non-covalent “π–π” interactions between the phenoxy groups on the dendrimeric compound 5 and the extended π system of the MWCNTs. The MWCNT-5 hybrid exhibited significant dispersion stability in common organic solvents.