The palladium(0)-catalyzed Heck cross coupling reactions of 1-bromopyrene provided functionalized alkenylpyrenes with styrenes and acrylates by single fold Heck reactions. Suzuki-Miyaura cross coupling reactions of the differently substituted di and mono fluoro benzenes with different arylboronic acids afforded fluoro-substituted terphenyls with excellent site-selectivity. Sonogashira and Suzuki-Miyaura coupling reactions of 1,2-difluoro, 1,3-difluoro, 1,4-difluoro, 1-fluoro, tetraiodobenzenes and pentaiodobenzenes respectively provided tetra- and penta-alkynylated and arylbenzene products.