Simultaneous measurements of atmospheric organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) were made at four sampling sites, namely Guangzhou (GZ), Zhaoqing (ZQ), PolyU Campus (PU) and Hok Tsui (HT), in the Pearl River Delta (PRD) region between 14 August 2006 and 28 August 2007. The highest concentrations of total carbon (TC) were found at the medium-scale roadside site (PU) and the lowest were found at the regional-scale site (HT). Among the four sampling sites, the average WSOC at ZQ showed the highest concentrations, while the lowest were seen at HT. OC and EC concentrations revealed spring/summer minima and autumn/winter maxima at all sites except PU, which had a consistently high EC concentration all over the year. The highest WSOC/OC ratio was found at ZQ with an average of 0.41, suggesting that the OC was more oxidized in the atmosphere of the semi-rural site. The lowest WSOC/OC was found at the roadside site of PU. Moreover, the WSOC/OC ratio increased in autumn, when the photochemical reactions are the most active in the PRD region. This can be attributed to aging and atmospheric processing of the organic compounds during their transportation, or to the formation of secondary organic aerosol (SOA). Average annual secondary organic carbon (SOC) concentrations in PM2.5 were estimated to be 2.2 and 3.5 μg m−3 for GZ and ZQ, comprising 33.5% and 42.8% of the corresponding OC concentrations, respectively. The results indicate that SOC is significant in the PRD region, and its formation mostly occurs within the region.