AbstractSuspended particulate matter (SPM) collected in the urban area of Tokyo was analyzed using a transition edge sensor (TES) microcalorimeter x‐ray detector mounted on a FE‐SEM system. This prototype microcalorimeter spectrometer with an energy resolution of 19 eV identified some severe peak overlaps in the spectra measured by the traditional Si(Li) solid state detector, including S Kα with Pb Mα, Zn Lα with Na Kα, and Ti Kα with Ba Lα. In addition, the TES microcalorimeter showed good spatial resolution for the microanalysis of SPM. The focused ion beam(FIB) was successfully applied to fabricate a cross section of a single SPM particle. The chemical compositonal difference between surface and inner parts, and among different surface parts of the SPM was also determined. Through combination of the FIB technique and the TES microcalorimeter, we achieved a better understanding of the SPM. Copyright © 2009 John Wiley & Sons, Ltd.