© 2020, The Author(s). Radiocaesium-bearing microparticles (CsMPs), which are substantially silicate glass, were formed inside the damaged reactor and released to the environment by the Fukushima Dai-ichi Nuclear Power Plant accident in March 2011. The present study reports several valuable findings regarding their composition and structure using advanced microanalytical techniques. X-ray absorption near-edge structure of Fe L3-absorption indicated that the oxidation state of the iron dissolved in the glass matrix of the CsMPs was originally nearly divalent, suggesting that the atmosphere in which the CsMPs were formed during the accident was considerably reductive. Another major finding is that sodium, which has not been recognised as a constituent element of CsMPs thus far, is among the major elements in the glass matrix. The atomic percent of Na is higher than that of other alkali elements such as K and Cs. Furthermore, halite (NaCl) was found as an inclusion inside a CsMP. The existence of Na in CsMPs infers that seawater injected for cooling might reach the inside of the reactor before or during the formation of the CsMPs. These results are valuable to infer the environment inside the reactor during the accident and the debris materials to be removed during the decommissioning processes.