Long uniaxial edge-on nanocolumnar stacks of dodecyl-substituted hexa-peri-hexabenzocoronene grow spontaneously at the liquid/solid interface as a result of a hierarchical self-assembly process. Supramolecular multilayered architectures as complex as {HOPG/face-on/edge-on/edge-on} and {HOPG/face-on/edge-on/face-on} are produced, paving the way towards future applications in organic nanodevices. [GRAPHICS]