In this research, the influence of natural zeolites obtained from the volcanic ash of the Ubinas volcano has been studied as synergistic agents in a flame-retardant system (composed of ammonium polyphosphate, pentaerythritol, and polypropylene). Four zeolites were synthesized from volcanic ash, including those that had been calcined and those that had not. These were then placed in an alkaline solution at three synthesis temperatures. Zeolites were characterized through X-ray diffraction, specific surface area by nitrogen adsorption analysis (Brunauer–Emmett–Teller) and scanning electron microscopy. Polypropylene matrix composites were prepared with ammonium polyphosphate, pentaerythritol and zeolites at 1, 5 and 9%. Its thermal stability and fire resistance were evaluated by thermogravimetric analysis, limiting oxygen index, vertical burning test and cone calorimeter and its morphological structure by scanning electron microscopy. It was determined that the synthesis temperature and the use of calcined and without calcined volcanic ash have an influence on the characteristics of the zeolites and on its synergistic action.