Coal combustion from power stations is one of the largest contributors of potentially toxic trace elements to the environment. Some trace elements may be released in range of valencies, often with varying toxicity and bioavailability. Hence, determination of trace element speciation in coals and their combustion products is important for conducting comprehensive risk assessments of the emissions from coal-fired power stations. This study focuses on speciation of selected trace elements, As, Cr, and Se, in coal combustion products and Hg in flue gas, which were sampled at one Australian power station. Results showed that As, Cr and Se are all present in a range of valency states in coal. Concentrations of As and Se in the bottom ash as well as the more toxic hexavalent chromium were less than the detection limits. Fly ash contained the more toxic As³⁺ form at 10% of total arsenic, while selenium was mainly found in Se⁴⁺ form. Hexavalent chromium (Cr⁶⁺) in fly ash was 2.7 % of the total fly ash chromium. Mercury speciation in flue gas was determined using the Ontario Hydro sampling train and analysis technique. Approximately 58% of the total mercury in flue gas was released in the elemental form (Hg⁰), which has the highest residence time in the environment among all mercury species.