The overall process of coal combustion takes place in two successive steps: devolatilization and char combustion. The fate of sulfur during the devolatilization of coal of different rank was investigated. The significance of the investigation is in fact that a major part of sulfur release occurs during devolatilization of coal, (i.e., emission of sulfur oxides during combustion of coal largely depends on sulfur release during devolatilization). The experimental investigations were conducted to obtain the data about the quantitative relation between sulfur content in the coal and sulfur content in the char. Standard procedures were used for obtaining the chars in a laboratory oven and determining the sulfur forms in the coal and char samples. The experiments were done with grounded coal samples (< 0.2 mm), at the temperatures in the range of 500-1000 degrees C. We showed that the amount of sulfur remaining in the char decreases, but not significantly in the temperature range 600-900 degrees C. On the basis of the theoretical consideration of behavior of sulfur forms during devolatilization, certain simplifying assumptions, and obtained experimental data, we propose two correlations to associate the content of sulfur in the coal and in the char. The correlations are based on the results of the proximate analysis and sulfur forms in coal. Good agreement was found when the proposed correlations were compared with the experimental results obtained for investigated coals. Moreover, the correlations were verified by results found in the literature for numerous Polish, Albanian, and Turkish coals. Significant correlations (P < 0.05) between observed and calculated data with correlation coefficient, R > 0.9, were noticed in the case of all coals.