Measurements of excited and backscattered fluorescence radiation intensity were applied for ash content determination in coal samples. Si(Li) detector and low energy X-and gamma ray sources Fe-55, Cd-109, Pu-238, Am-241 were used. The measurement facility consisting of argon filled proportional counter and a Pu-238 radiation source was tested and compared, as generally used radioanalytical method, for ash content determination. The evaluation of results was based on the Snedecor F test and the analysis of the root mean square of estimate. The best results were obtained when Fe-55 source was used. In the multivariate linear regression independent variables SiK₉₇, CaK* lalpha*s and backscattered radiation intensities have been selected as variables that are best related with ash content in coal.