The number of coal-fired power plant in Java has been increased because of the government policy to supply the electricity in Indonesia to meet the electricity needs. This mega project is assumed to have an impact on the environmental and human health. In this study, the assessment of the air quality near the coal fired power plant has been carried out through characterization of the fine particulate matters. The particulate matters PM2.5 were collected in four sites in the vicinity of coal-fired power plant in Banten, West Java and Central Java, Indonesia. The elemental concentrations in PM2.5 such as Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb have been identified using energy dispersive X-ray Fluorescence-EDXRF. The validation of XRF measurement was applied using standard reference material NIST SRM 2783 Air Particulate on Filter Media. The elemental concentration of PM2.5 especially for the toxic elements as well as the mass and black carbon were compared between four sites. For some sites, the level of elemental concentrations was lower than other industrial sites in Java, due to the sampling was carried out before the commissioning/normal operation. Further and periodical monitoring will be needed to obtain a better comprehensive result to assess the impact of coal power plant to the surrounding environment.