Fluorenes have been synthesized through an efficient novel Pd-catalyzed tandem cross-coupling reaction; these substrates are fascinating building blocks found in organic photoelectric materials. The position of the substituent on fluorenes could be conveniently tuned by changing the halogen in the ortho-halobenzyl bromide substrates when coupled with various arylboronic acids. This newly developed synthetic approach could achieve the potential diversity in fluorene-based molecular architectures.