Microparticles of radioactive cesium (Cs)-bearing silicate glass emitted from the Fukushima Daiichi nuclear power plant were investigated mainly using state-of-the-art energy-dispersive X-ray spectroscopy in scanning transmission electron microscopes. Precise elemental maps of the particles were obtained using double silicon drift detectors with a large collection angle of X-rays, and qualitative elemental analysis was performed using high-resolution X-ray spectroscopy with a microcalorimetry detector. Beside the substantial elements (O, Si, Cl, K, Fe, Zn, Rb, Sn and Cs) as previously reported, Mn and Ba were also common, though their amounts were small. The atomic ratios of the substantial elements were not the same but varied among individual particles. Fe and Zn were relatively homogeneously distributed, whereas the concentration of alkali ions varied radially. Generally, Cs was rich and K and Rb were poor outward of the particles but the degree of such radial dependence was considerably different among the particles. A concentration of Sn on the particle surface was observed. High-resolution imaging indicated the formation of SnO2 (cassiterite) nanocrystals on the surface. Synthesis of the bulk glass with a similar composition to the microparticles was attempted by quenching the silicate melt from ∼1600°C. However, homogeneous silicate glass like that of the microparticles could not be obtained due to the segregation of nano-spherules rich in Fe and Zn, suggesting that the microparticles were formed in a very specific condition in the nuclear reactor.