Polypyridyl-functionalized alkynes are a class of bifunctional ligands and very useful for the design of heteropolynuclear or multicomponent arrays as optoelectronic materials at the molecular level. This article focuses on reviewing the recent progress in design of luminescent heteropolynuclear or multicomponent complexes composed of photoactive discrete subunits using 2,2′-bipyridyl, 1,10-phenanthroline or 2,2′:6′,2″-terpyridyl functionalized alkynyl ligands with both acetylide and polypyridyl groups. The preparation, molecular fabrication, structural features, and spectroscopic and luminescent properties are summarized to elucidate the correlation of structure and photophysical properties as well as triplet energy transfer between two or more photoactive organometallic subunits.