Fly ash has been utilized as a reinforcing material in the production of aluminum matrix composites, and in this investigation, Al-Si (LM6) fly ash composites were fabricated using the compocasting method. Various compositions of fly ash were incorporated into the samples (4, 5 and 6 wt%), and the preparation temperature ranged from 560 to 800 °C. This study investigated the thermal (CTE and DTA) and chemical properties (XRD) of fly ash reinforcement and the aluminum melt in the composites. The results revealed that composites with 5 wt% of fly ash exhibited the lowest CTE value compared to those with 4 and 6 wt%. This observation was corroborated by XRD analysis, indicating a reaction between the fly ash particles and the aluminum melt. However, the DTA analysis did not find a significant impact of the addition of fly ash on the melting temperature of the prepared composites. In contrast, this study identified and investigated the existence of reaction effects between the fly ash particles and the aluminum melt.