Multi-walled carbon nanotubes (CNTs) were prepared over a series of W-doped Co-based catalysts derived from layered double hydroxide precursor by catalytic chemical vapor deposition (CCVD) of acetylene. The materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption.desorption experi-ments and Raman spectroscopy. The effect of the proportion of W in the Co-based catalysts on the carbon yield, diameter uniformity and quality of CNTs was investigated. The results demonstrated that with the increasing W/Co molar ratio from 0 to 1.0, both the mean number of walls and the average diameter of CNT produced over catalysts increased from about 8 to 28 nm and from about 12.1 to 23.7 nm, respectively. A small amount of tungsten added to the catalyst with the W/Co molar ratio of 0.3 could facilitate the dispersion of catalytically active Co species on the surface of support, and thus uniform and high-quality CNTs with a remarkably high yield of ca. 1600% were obtained.