Acid deposition has been regarded as a serious factor in the deteriorative water environment and ecosystems. Despite the powerful acid emission control measures have been implemented by the Chinese government, many areas (especially Southeast China) are still suffering from acid deposition. The chemical and isotopic (delta S-34 and Sr-87/ Sr-86) compositions of rainwater in Hangzhou, a typical megacity in Southeast China with serious acid rain problem, for one year were studied with the aim to better constrain potential sources and explore the causes of rainwater acidification. Most rainwater samples were acidic, with a VWM pH value of 4.65. SO42- was the dominant anion and the main acid ion in rainwater. Sulfur isotope and the quantity equilibrium model revealed that sea salt, crustal, biogenic, and anthropogenic sulfur represented 2.3%, 0.1%, 16.7%, and 80.8% of the SO42- source in rainwater, respectively. The back trajectory and strontium isotopes indicated that the base cations (BCs) in rainwater originated mainly from anthropogenic sources. The relatively low neutralizing capacity caused by limited BCs input and emission control measures undermines some efforts to reduce rainwater acidity. This case study demonstrated that a valuable tool to probe the source of acid rain and unravel the mechanism of rainwater acidification can be provided by multiple lines of evidence, including rainwater chemical compositions, stable sulfur isotopes, and stable strontium isotopes.