A variety of functionalized penta-arylcorannulene derivatives were prepared in high yields and high chemoselectivity by a cross-coupling reaction between sym-pentachlorocorannulene and substituted arylboronic acids using Fu's Pd(0) catalyst. This approach provides a general entry to penta-substituted corannulene derivatives, which are useful building blocks for various structures of high complexity, such as pentagonal dendrimers, synthetic capsids, and discotic liquid crystals. This was demonstrated here by the facile synthesis of a third generation pentagonal dendrimer.