The present study assessed the multi-year behaviours of high molecular-weight PAHs (four or more benzene ring) (benzo(a)anthracene, benzo(a)pyrene (BaP), benzo(b)fluoranthene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, and indeno(1,2,3-cd)pyrene) that are associated with airborne particulates in five areas of three cities (Seoul, Ulsan, and Gwangyang) and one rural area (Taeahn), utilizing four-year monitoring data. The order of the mean PAH concentrations was as follows (in descending order) residential-commercial complex (Seoul), traffic junction (Seoul), petrochemical plant (Ulsan), iron and steel plant (Gwangyang), and background area (Taeahn). With a few exceptions, individual congeners exhibited a concentration pattern similar to that of the total PAHs. The high PAH concentrations in the residential-commercial complex and traffic junction are likely attributable to the heavy traffic in Seoul, South Korea’s capital. The inter-annual and seasonal modulations of PAHs were different for each area type, due to differences in land use. It is suggested that neither total PAHs nor BaP alone seem sufficient to index carcinogenicity associated with exposure to these substances. In most cases, the three meteorological parameters (relative humidity, temperature, and wind speed) exhibited a negative correlation with PAH concentrations, although only a few cases demonstrated a statistical significance at p < 0.05.