Synthesis and alignment of three dimensional architectures of carbon nanotubes (CNTs) is demonstrated. Their formation starts from nanoscaled catalysts and interaction with reactive carbon species generated from a hydrocarbon source. The process leads to large spatially oriented CNTs with a high aspect ratio and offers the possibility to transfer these structures to variable substrates. Such CNT nanostructures represent hierarchical materials which allow to bridge the gap from nano to micro to macro dimensions. Engineering the surface of these 3D aligned CNT structures allows tailoring their surface wetting behavior from superhydrophilic to superhydrophobic.