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The first example of a directed and regioselective arylation of polycyclic aromatic hydrocarbons (PAHs) by using a P＝O directing group is reported herein. The protocol uses a cheap copper catalyst, and results in a breakthrough meta-selective C–H functionalization of arylphosphine oxide compounds. Substrates with potential fluorescence properties, for example, pyrene and fluoranthene, were successfully arylated under the system, thus achieving an efficient modification of fluorescent molecules containing the P＝O functional group. [ABSTRACT FROM AUTHOR]