For the purpose of systematically characterizing the ambient volatile organic compound (VOC) levels and their emission sources in the Pearl River Delta (PRD) of China, a grid study with VOC samples simultaneously taken at 84 sites over the PRD was conducted in summer and winter of 2008 and 2009. Positive Matrix Factorization (PMF) model was applied to identify the major VOC contributing sources and their temporal and spatial variations. Nine sources were identified, with gasoline exhaust, industrial emission and LPG leakage 82 propellant emission the top three significant sources. They accounted for 23%, 16% and 13% of the ambient VOC levels, respectively. Control measures should be therefore targeted on mitigating the VOC emissions from the traffic-related and industrial-related sources. The total VOC level did not show strong increase from 5 a.m. to 10 a.m. during all the four sampling campaigns, which may result from stronger wind and higher mixing height at 10 a.m. Three hotspot areas with significant VOC contributions were identified by source apportionment analysis: (1) the Pearl River Estuary; (2) an area from Central Dongguan to North Shenzhen; and (3) the Zhuhai-Zhongshan-Jiangmen area. For better characterizing the roles of VOC and NO, in producing the secondary pollutants and to identify specific sources emitting excessive concentrations of precursors, the emission-oriented Photochemical Assessment Monitoring Station (PAMS) network is recommended to be established in the PRD. Three PAMS networks are suggested in correspondence to the three identified hotspot areas. (C) 2012 Elsevier Ltd. All rights reserved.