Chemical characterization of particulate matter (PM) to which human populations are exposed is essential to developing an understanding of the risks and associations of PM with health endpoints. In this research we developed microanalysis methods for the characterization of personal exposure to PM and demonstrated the capabilities of sensitive analytical techniques through the analysis of 9 aerosol samples. These techniques will be used in future exposure assessment studies and to conduct source apportionment of personal and community exposures. Aerosol loadings comparable to 24-h personal exposure samples (150–480 μg) were collected on 25 mm Teflon filters with a PM10 personal sampler operating at 4 lpm. Qualitative functional group identification as well as quantitation of five metals (V, Cr, As, Cd, Pb) and 26 polycyclic aromatic hydrocarbons (PAHs) present in the aerosol samples was accomplished using the following techniques: Fourier Transform Infrared (FTIR) Spectroscopy, Inductively-Coupled Plasma/Mass Spectrometry (ICP/MS), and Gas Chromatography/Mass Spectrometry (GC/MS). Signals characteristic of particles from cigarette smoke and cooking were identified. The detection limits of ICP/MS and GC/MS were < 0.01–8.3 ng, with most detection limits below 1 ng.