One of the most distinct characters of aryne chemistry over other synthetic methodologies is its ability to simultaneously functionalize the vicinal two positions of a benzene ring with diverse combinations of substituents. Moreover, the functionalization of the remaining four positions can be also achieved through multiaryne equivalents, in which more than one triple bond is generated on the different locations of the same benzene ring. This tutorial review summarizes the applications of benzdiyne and benztriyne equivalents from the standpoint of synthetic organic chemistry as well as in the preparation of polycyclic aromatic functional frameworks.