A series of macrocyclic compounds, [6]cyclo-2,7-naphthylenes ([6]CNAP), composed of six naphthylene units are synthesized through a [3+3] convergent route in good to moderate yields. The synthesis method allowed for the introduction of dicarboxylic imide moieties to the naphthylene units. Crystallographic analysis of a derivative possessing four imide groups showed a trimeric columnar assembly with an alignment of nanometer-sized macrocyclic pores.