The article presents the test results of the co-firing process of a glycerine fraction derived from the production of liquid biofuels (fatty acid methyl esters) with coal. The test was performed in industrial conditions using a steam boiler with a capacity of approx. 2 MW in one of the building materials manufacturing facilities. The process of co-firing a mixture of a 3% glycerine fraction and eco-pea coal was evaluated. The reference fuel was eco-pea coal. The combustion process, composition and temperature of exhaust gases were analyzed. Incorrect combustion of glycerine fraction may result in the emission of toxic, mutagenic, and carcinogenic substances, including polycyclic aromatic hydrocarbons. During the test of the combustion process of a mixture of glycerine fraction and eco-pea coal, a decrease in the content of O2, CO, and NOx was observed as well as an increase in the content of H2, CO2, and SO2 in the fumes and growth of temperature of exhaust gases in relation to the results of combustion to eco-pea coal. Reduced content of carbon monoxide in exhaust gases produced in the combustion could be caused by the high temperature of the grate or by an excessive amount of oxygen in the grate. The higher content of oxygen in glycerine changes the value of excess air coefficient and the combustion process is more effective. The bigger content of sulfur dioxide in burnt fuels containing the glycerine fraction could be caused by the presence of reactive ingredients contained in the glycerine fraction. The reduced content of nitrogen oxides in exhaust gases originating from the combustion of a fuel mixture containing a fraction of glycerine could be caused by lower content of nitrogen in the glycerine fraction submitted to co-firing with coal and also higher combustion temperature and amount of air in the combustion chamber. The increased content of carbon dioxide in exhaust gases originating from the combustion of fuel mixture containing glycerine fraction could be caused by the influence of glycerine on the combustion process. The increase of hydrogen in the glycerine fraction causes the flame temperature to grow and makes the combustion process more efficient.