The working of thermal power plant (TPP) in an area is the primary source of pollution, because it releases potentially toxic elements (PTEs) laden fly ash (FA), which may lead to serious health and ecological risks. This study assessed the current status of pollution in the nearby areas of TPP by measuring the concentration of PTEs (As, Cd, Cr, Hg, and Pb) in FA, soils (roadside, forest, agricultural, and residential areas), tree leaves (Albizia lebbeck and Madhuca longifolia), and vegetables (Raphanus sativus and Allium cepa). Hg concentration in FA was found to be lower (0.449 mg/kg) than global average Hg content (0.62 mg/kg). PTEs content in topsoil (0–15 cm) of the roadside area was comparatively higher (As, 4.56; Cd, 12.68; Cr, 72.53; Hg, 2.77; Pb, 46.05 mg/kg) than other areas. Bioaccumulation coefficient and transfer factor of As in M. longifolia and A. cepa were 1.03 and 0.30, respectively, which showed high accumulation of PTE. The ecological risk index (1561) was found to be very high in the roadside area, due to high values ecological risk factor of Cd (1268) and Hg (277) in the area. The total hazard quotients (THQs) posed by As, Cd, Cr, and Pb in vegetables were exceeding the safe limits (THQ > 1), suggesting that long-term consumptions of these vegetables may pose serious health risks. Therefore, the remediation measures are needed to minimize the pollution level in soil to reduce the health risk due to the exposure of PTEs.