Ambient coarse particles (diameter 1.8-10 μm), fine particles (diameter 0.1-1.8 μm), and ultrafine particles (diameter < 0.1 μm) in the atmosphere of the city of Shanghai were sampled during the summer of 2008 (from Aug 27 to Sep 08). Microscopic characterization of the particles was investigated by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDX). Mass concentrations of Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Rb, Sr, and Pb in the size-resolved particles were quantified by using synchrotron radiation X-ray fluorescence (SRXRF). Source apportionment of the chemical elements was analyzed by means of an enrichment factor method. Our results showed that the average mass concentrations of coarse particles, fine particles and ultrafine particles in the summer air were 9.38 ± 2.18, 8.82 ± 3.52, and 2.02 ± 0.41 μg/m3, respectively. The mass percentage of the fine particles accounted for 51.47% in the total mass of PM10, indicating that fine particles are the major component in the Shanghai ambient particles. SEM/EDX results showed that the coarse particles were dominated by minerals, fine particles by soot aggregates and fly ashes, and ultrafine particles by soot particles and unidentified particles. SRXRF results demonstrated that crustal elements were mainly distributed in the coarse particles, while heavy metals were in higher proportions in the fine particles. Source apportionment revealed that Si, K, Ca, Fe, Mn, Rb, and Sr were from crustal sources, and S, Cl, Cu, Zn, As, Se, Br, and Pb from anthropogenic sources. Levels of P, V, Cr, and Ni in particles might be contributed from multi-sources, and need further investigation.