Fine particle associated with haze pollution threatens the health of more than 400 million people in China. It is therefore of great importance to thoroughly investigate and understand its composition. To determine the physicochemical properties in atmospheric fine particles at the micrometer level, we described a sensitive and feasible surface-enhanced Raman scattering (SERS) method using Ag foil as a substrate. This novel method enhanced the Raman signal intensities up to 10,000 a.u. for ν(NO₃^−) in fine particles with an enhancement factor of at least 56. The SERS effect of Ag foil was further studied experimentally and theoretically and found to have an enhancement factor of the order of ~ 104. Size-fractionated real particle samples with aerodynamic diameters of 0.4–2.5 µm were successfully collected on a heavy haze day, allowing ready observation of morphology and identification of chemical components, such as soot, nitrates, and sulfates. These results suggest that the Ag foil based SERS technique can be effectively used to determine the microscopic characteristics of individual fine particles, which will help to understand haze formation mechanisms and formulate governance policies.