In this study, we report on a unique, one-step fabrication technique enabling the simultaneous synthesis of vertically aligned multi-walled carbon nanotubes (VA-MWCNTs) with dual height scales through alcohol catalyzed chemical vapor deposition (ACCVD). Regions of VA-MWCNTs with different heights were well separated from each other leading to a self-patterning on the surface. We devised a unique layer-by-layer process for application of catalyst and inhibitor precursors on oxidized Si (100) surfaces before the ACCVD step to achieve a hierarchical arrangement. Patterning could be controlled by adjusting the molarity and application sequence of precursors. Contact angle measurements on these self-patterned surfaces indicated that manipulation of these hierarchical arrays resulted in a wide range of hydrophobic behavior changing from that of a sticky rose petal to a lotus leaf.