The effect of catalyst addition on ignition and combustion characteristics of biomass fuels from the Mediterranean region, one lignite and lignite/biomass blends, were investigated. Transition metal oxides and alkali/alkaline earth compounds were used as catalysts. The experiments were conducted in a thermogravimetric analysis system. The performance of the process was evaluated in terms of combustion rate, ignition, and combustion indices. The results showed that metal oxides enhanced the ignition and combustion performance of lignite, showed no catalytic activity to burn off of biomass fuels, but influenced the temperature sensitivity of their reaction in air. The relative activity was in the following order: V2O5>Fe2O3>CaO>NaCl>MgO>CuO>TiO2>LiCl. The combustion characteristics of the blends followed those of parent fuels in an additive manner. Blending lignite with biomass fuels increased its thermochemical reactivity. In terms of burnout, catalyzed combustion of blends was further improved.