This paper analyses the influence of the inner structure of a SiO₂ coating deposited on SiC particles by a sol-gel route on reactivity and wettability between SiC particles and molten aluminium during composite manufacturing. Different heat treatments were applied to the sol-gel coatings to change the porous structure of the amorphous silica. The coatings subjected to the mildest heat treatment were more reactive with molten aluminium, enriching the Si content of the matrix composite, and hence inhibiting direct reaction of the SiC particles and the formation of aluminium carbide. Thermal analysis showed that Si enrichment altered the solidification behavior of the aluminium matrix and its resultant microstructure, influencing the manufacturing conditions and final properties of the fabricated composites.