The C-H annulative coupling of benzaldehydes, anilines, and alkynes catalyzed by different co-catalysts ([CpRhCl2]2, Cu(OAc)2, and AgBF4) efficiently generates complex polycyclic aromatic hydrocarbons, including ladder molecules, in a highly adaptable and modular fashion. To evaluate the compatibility of the anchor group -SMe, we synthesized the short ladder molecule L1-PF6 from 4-(methylthio)benzaldehyde, 4-(methylthio)aniline, and diphenylacetylene in 87% yield (Fig. ). Additional diarylalkyne and dialkylalkyne substrates were also efficiently tolerated in this multicomponent reaction. Post-annulation ion exchange reactions conveniently generated an expanded library of ladder compounds .