AbstractThe stepwise palladium‐catalyzed coupling of dibromo‐1,6‐methano[10]annulene derivatives to a phenyl‐acetylene substituted by an electron‐withdrawing group followed by coupling with a phenylacetylene possessing an electron‐donating group allows the preparation of donor/acceptor systems which contain three aromatic moieties linked by ethynediyl bridges. The same type of cross‐coupling starting from 2‐ethynyl‐1,6‐methano[10]annulene and bromo‐substituted azobenzene derivatives provides easy access to a new class of azo dyes. The properties of these compounds are compared to those of analogous compounds containi