This paper presents the results of a multifaceted analysis of the application of catalytic additives to hemp pellets’ combustion in a low-power boiler. The research concerns the effects of five catalytic additives applied inside the boiler’s combustion chamber—based on TiO2, MnO2, Cu(NO3)2 × 3H2O, H2PtCl6 solution, and 99.5% pure urea solution—on the quality of hemp pellets’ combustion process. For this purpose, technical and elemental analyses of the used fuel were performed. The chemical composition of exhaust gases (NOx, CO, SO2, and PM content) was also examined using an exhaust gas analyzer and a dust meter. The highest reductions in emissions of individual pollutants were for CO (−113%; combustion with Ad3), NOx (−66%; combustion with Ad 4), SO2 (−48%; combustion with Ad3), and PM (−78%; combustion with Ad1). The study also determined the amount of avoided costs due to the use of catalytic additives, as well as the annual prevented CO2 emissions to the atmosphere. Due to rising fuel and energy prices, this study could be helpful for biomass boiler owners who would like to burn locally available raw materials and increase the combustion process’ efficiency.