The application of a new benzannulation reaction for the regiocontrolled synthesis of functionalized chrysenes is reported. The initial benzannulation and the subsequent halogen displacement reactions are both highly regiospecific, which thereby enables the regiocontrolled synthesis of a variety of 4,10-disubstituted chrysenes from commercially available 1,5- dihydroxynaphthalene. 4,10-Dichlorochrysene, which is itself readily available from 1,5-dihydroxynaphthalene, undergoes facile displacement reactions with a variety of nucleophiles to afford 4,10-disubstituted chrysene derivatives. © 2013 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.