Self-aligned arrays of long multi-walled carbon nanotubes (MWCNT) were grown by chemical vapor deposition (CVD) from a gas mixture of C2H4-H2-Ar-H2O at 750°C. A catalytically active alumina surfaces coated with a thin layer of iron and supported by a Si/SiO2 substrate were prepared using pulsed laser deposition method. Combinatorial approach has been used for optimization of catalytic properties of the multilayered system Si/SiO2/Al2O3/Fe. Sixteen different combinations of catalytic surfaces having thicknesses of Fe (0, 1, 2, and 3 nm), alumina (0, 10, 20 and 30 nm) per sample were deposited on two Si/SiO2 substrates with silica thickness 150 and 500 nm. To study the effect of alumina phase on efficiency of catalytic surfaces two substrate temperatures 200 and 700°C were used to produce amorphous and γ-alumina phases correspondingly. This approach allowed the optimal structure of catalytic surface to be determined from 64 different substrates on 4 samples in a single MWCNT growth experiment, for a given set of processing conditions. It was found that most efficient growth of MWCNT arrays on amorphous alumina occurred at Fe nanolayer thickness of 2 nm while catalyst having γ-alumina layer has tendency to be more efficient at higher thickness of Fe. Catalytic substrate containing amorphous alumina has less sensitivity to thickness of iron while γ-alumina based catalyst has significant variation in catalytic activity with change of iron content.