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The combustion process of Albizia falcataria (AF) sawdust with the addition of natural zeolite (NZ) was observed experimentally using PT 1600 LINSEIS Simultaneous thermal analyzer (STA). The results showed that alkali metal and alkaline metal earth in NZ play an essential role in the process of decomposing the Hemicellulose AF molecule. The results of the molecular analysis show that the chemical balance of the mixture determines the combustion temperature. Excess NZ becomes a thermal burden which slows down the combustion reaction because heat does not sufficiently activate alkali metal and alkaline metal earth in NZ. In a small amount, NZ is less involved in the AF decomposition process. It shows that a mixture of AF and NZ can increase combustion kinetic in the right mix. Addition of 15–20% of NZ decreases the ignition temperature within faster burning rate. Activated alkali metal and alkaline metal earth decompose hemicellulose faster so that they burn completely in minimizing pollutant and maximizing LHV. Greater NZ completes the decomposition much earlier so that at the resting time of the process NZ slightly absorbs heat sinking LHV. The drastic reduction of Ca due to NZ make the fuel is suitable for boiler because Ca is responsible for agglomeration and corrosion.