Shape-persistent macrocycles with interiors in the nanometer regime were prepared by the oxidative cyclization of the appropriate bisacetylene precursors under high-dilution conditions. These compounds contain polycyclic aromatic hydrocarbons in the ring backbone and are decorated with extra annular oligoalkyl or silyl side groups. Interestingly, after depositing them on different surfaces and investigating the self-assembled structures by means of scanning tunneling microscopy (STM) and atomic force microscopy (AFM), various nanostructures were observed. STM showed that these macrocycles are organized in two-dimensional (2D) layers, whereas AFM showed, in addition, the formation of 2D crystallites and one-dimensional fibrils. These results reveal the importance of the extra annular substitution of the macrocycles in creating patterned surfaces and nanoscale objects.