PM2.5 samples were collected at six general stations and one roadside station in Hong Kong in two periods of high particulate matter (PM) in 2003 (27 October–4 November and 30 November–13 December). The highest PM2.5 reached 216 μg m−3 during the first high PM period and 113 μg m−3 during the second high PM period. Analysis of synoptic weather conditions identified individual sampling days under dominant influence of one of three types of air masses, that is, local, regional and long‐range transported (LRT) air masses. Roadside samples were discussed separately due to heavy influences from vehicular emissions. This research examines source apportionment of fine organic carbon (OC) and contribution of secondary organic aerosol on high PM days under different synoptic conditions. Six primary OC (POC) sources (vehicle exhaust, biomass burning, cooking, cigarette smoke, vegetative detritus, and coal combustion) were identified on the basis of characteristic organic tracers. Individual POC source contributions were estimated using chemical mass balance model. In the roadside and the local samples, OC was dominated by the primary sources, accounting for more than 74% of OC. In the samples influenced by regional and LRT air masses, secondary OC (SOC), which was approximated to be the difference between the total measured OC and the apportioned POC, contributed more than 54% of fine OC. SOC was highly correlated with water‐ soluble organic carbon and sulfate, consistent with its secondary nature.