Using Al2O3 support layer with certain morphology and annealing under H2, catalyst NP with small size and narrow size distribution can be formed. Differentiated study on the effect of different bilayer Co‐Mo catalyst configuration on the properties of grown SWCNTs. Lowering catalyst deposition rate is a straightforward approach to fabricate catalyst layer with low surface roughness and small NP size. Bilayer Co‐Mo:0.5‐0.1 nm prepared by low catalyst deposition rate shows a high potential for future applications.