Multi-walled carbon nanotubes (CNTs) were prepared by thermal chemical vapor deposition (CVD) and microwave plasma chemical vapor deposition (MPCVD) using various combination of binary catalysts with four transition metals such as Fe, Co, Cu, and Ni. In the preparation of CNTs from acetylene precursor by thermal CVD, the CNTs with very high yield of 43.6 % was produced over $Fe-Co/Al_2O_3$. The highest yield of CNTs was obtained with the catalyst reduced for 3 hr and the yield was decreased with increasing reduction time to 5 hr, due to the formation of $FeAl_2O_4$ metal-aluminate. On the other hand, the CNTs prepared by acethylene plasma CVD had more straight, smaller diameter, and larger aspect ratio(L/D) than those prepared by thermal CVD, although their yield had lower value of 27.7%. The degree of graphitization of CNTs measured by $I_d/I_g$ value and thermal degradation temperature were 1.04 and $602^{circ}C$, respectively.