Particulate matter (PM) air pollution is a central concern for public health. Current legislation relies on a mass concentration basis, despite broad acceptance that mass alone is insufficient to capture the complexity and toxicity of airborne PM, calling for additional and more comprehensive measurement techniques. We study to what extent scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDS) can be applied for physicochemical characterization of complex aerosols, and investigate its potential for separating particle properties on a single particle basis, even for nanosized particles. SEM/EDS analysis is performed on impactor samples of laboratory generated aerosols, consisting of either NaCl, Halloysite fibers, soot-like Printex90 agglomerates, or their combination. The analysis is automated and performed as EDS maps, covering a statistically relevant number of particles, with analysis times of approximately one hour/sample. Derived size distributions are compared to scanning mobility particle sizer (SMPS) and electric low-pressure impactor (ELPI) results. A method is presented to estimate airborne number concentrations and size distributions directly from SEM results, within a factor 10 of SMPS and ELPI outcomes. A classification scheme is developed based on elemental composition, providing class-specific information with individual particle statistics on shape, size, and mixing state. This can identify primary particles for source apportionment and enables easy distinction between fibrous and dense particle classes, e.g. for targeted risk assessments. Overall, the SEM/EDS analysis provides a more detailed physicochemical characterization of PM than online measurements, e.g. SMPS and ELPI. The method has the potential to improve assessments of PM exposure and risk, and facilitates source identification, even without prior knowledge at sampling.