Pincer type aminomethylphosphine–Pd(II) complexes supported on multi-walled carbon nanotube (MWCNT) have been synthesized and characterized using X-Ray diffraction spectrometry, scanning electron microscopy, thermal analysis, energy dispersive X-Ray, Fourier transform infrared spectrometry, transmission electron microscopy (TEM) and ultraviolet–visible spectrometry techniques. The novel complexes were tried as catalysts in Heck C–C coupling reactions. The crystallite size and lattice strain of the MWCNT based compounds were calculated by the Scherrer’s equation. The optical parameters of the MWCNT based structures were analyzed and the band gap enhanced from 4.42 to 4.98 eV. Different solvents (toluene, 1,4-diooxane, DMF and NMP) and bases (Et3N, Na2CO3, NaOAc and K2CO3) were tried at different temperatures (80, 100 and 110 °C) in the cross-coupling of bromobenzene with styrene. The optimum yield was found in the presence of K2CO3, 110 °C in 1,4-dioxane solvent system.