Transition metals play an important role in the growth of carbon nanotubes (CNTs). Series of unsupported hybrid catalysts consisting of Ni:Cu, Ni:Cr, and Ni:Mn doped with Nd catalyst, respectively were synthesized by impregnation method. The catalytic performance of the catalyst for the production of CNTs was measured in the pyrolysis process of hydrocarbon source by catalytic chemical vapour deposition method. Acetylene gas was used as the source of carbon in the pyrolysis process. The decomposition of acetylene was carried out at 700ºC. The bulk properties of the catalysts were investigated by X-ray diffraction. Field emission scanning electron microscopy and thermal analysis were used to observe the morphology and thermal stability of the as-synthesized CNTs, respectively. Hybrid catalyst of Ni:Mn/Nd and Ni:Cr/Nd in 3:1 atomic ratio gave high percentage of carbon yield which was assigned for the high production of CNTs with the mass of yield 18 times greater than the initial mass of the catalyst used.