Corrosion effects in thermal power plants and environmental impact cause an increase in demand for fluorine analysis in coal. Solid sample decomposition, organic and inorganic fluorine compounds, volatility of fluorine species are problems which deserve a special attention. The aim of this work was to optimize the pyrohydrolytic (Phy) determination of fluorine content in the lignite coal. The parameters of pyrohydrolysis were evaluated and optimized by two statistical methods: Plackett-Burman (PB) design and response surface methodology (RSM). The content of fluorine in the absorption solution was measured by fluoride ion-selective electrode. The limit of detection of the proposed method was 20 mu g g(-1), with good recovery (95%) and relative standard deviation less than 5%. With such benefits as simplicity, precision, accuracy and economy, this method is highly suitable for routine analysis of coal. (C) 2010 Elsevier B.V. All rights reserved.