The Pearl River Delta region (PRD) of China has long suffered from severe ground-level ozone pollution. Knowledge of the sources of volatile organic compounds (VOCs) is essential for ozone chemistry. In this work, a speciated VOC emission inventory was established on the basis of updated emissions and local VOC source profiles. The top 10 species, in terms of ozone formation potentials (OFPs), consisted of isoprene, mp-xylene, toluene, ethylene, propene, o-xylene, 1,2,4-trimethylbenzene, 2-methyl-2-butene, 1-butene, and α-pinene. These species contributed only 35.9% to VOCs emissions but accounted for 64.1% of the OFP in the region. The spatial patterns of the VOC source inventory agreed well with city-based source apportionment results, especially for vehicle emissions and industry plus VOC product-related emissions. Mapping of the OFPs and measured ozone concentrations indicated that the formation of higher ozone in the south and southeast of the PRD region differed from that in the Conghua area, a remote area in the north of the PRD. We recommend that the priorities for the control of VOC sources include motorcycles, gasoline vehicles, and solvent use because of their larger OFP contributions.