Thallium is released into the biosphere from both natural and anthropogenic sources. It is generally present in the environment at low levels; however, human activity has greatly increased its content. Atmospheric emission and deposition from industrial sources have resulted in increased concentrations of thallium in the vicinity of mineral smelters and coal-burning facilities. Increased levels of thallium are found in vegetables, fruit and farm animals. Thallium is toxic even at very low concentrations and tends to accumulate in the environment once it enters the food chain. Thallium and thallium-based compounds exhibit higher water solubility compared to other heavy metals. They are therefore also more mobile (e.g. in soil), generally more bioavailable and tend to bioaccumulate in living organisms. The main aim of this review was to summarize the recent data regarding the actual level of thallium content in environmental niches and to elucidate the most significant sources of thallium in the environment. The review also includes an overview of analytical methods, which are commonly applied for determination of thallium in fly ash originating from industrial combustion of coal, in surface and underground waters, in soils and sediments (including soil derived from different parent materials), in plant and animal tissues as well as in human organisms.