The macrocyclization of 2,6-dialkoxynaphthalene monomers to prism[5]arenes is thermodynamically templated by DABCO cations. In this study, we demonstrate that a greater template affinity for prism[5]arene improves the macrocyclization yield. By using novel templating cations, the yield of alkoxy-prism[5]arenes increases significantly compared with those of previously reported procedures, while the purification process becomes easier and faster.