In the present letter, for the first time, the efficacy of hydrotalcite-like layered double hydroxides (LDHs) materials as alternative and novel catalyst precursors for the synthesis of carbon nanotubes (CNTs) via catalytic chemical vapor deposition (CCVD) of acetylene was reported. Nanometer-sized cobalt particles were prepared by calcination of a single molecular LDH precursor containing cobalt (II) and aluminum (III) and following by a process of reduction. Multi-walled CNTs with uniform diameters were obtained using the as-synthesized catalyst in the reaction.