Despite recent efforts to investigate the distribution and fate of polycyclic aromatic hydrocarbons (PAHs) in air, water, and soil, very little is known about their temporal change in wet deposition. As a result of increased attention to public health, a large-scale survey on the deposition flux and distribution of PAH contamination in rainwater was urgently conducted in Shanghai, China. In this study, 163 rainwater samples were collected from six sites, and 15 PAH compounds were detected by the use of a simple solid phase microextraction (SPME) technique coupled with gas chromatography-mass spectrometry. The dominant PAH species monitored were naphthalene, phenanthrene, anthracene, and fluoranthene. The concentration of total PAHs per event was between 74 and 980 ng/L, with an average value of 481 ng/L, which is at the high end of worldwide figures. The annual deposition flux of PAHs in rainwater was estimated to be 4148 kg/yr in the Shanghai area, suggesting rainfall as a major possible pathway for removing PAHs from the atmosphere. Diagnostic analysis by the ratios of An/178 and Fl/Fl+Py suggested that combustion of grass, wood, and coal was the major contributor to PAHs in the Shanghai region. Back trajectory analysis also indicated that the pollutant sources could be from the southern part of China.