Polymer-derived ceramics have shown promise as a novel way to process low-dimensional ceramics such as environmental barrier coatings. Composite coatings have been developed as oxidation and carburization barriers on steel using poly(hydridomethylsiloxane) matrix and titanium disilicide as reactive fillers. A systematic study of the phase transformations and microstructural changes in the coatings and their components during pyrolysis in air is presented here. The system evolves from an amorphous polymer filled with a binary metal at room temperature to an inorganic amorphous network of oxidized silicon and titanium at the target temperature of 800 °C. Crystallization of the composite occurs at higher temperatures to reach cristobalite and rutile by 1600 °C. The polymer-to-ceramic conversion occurs between 200 and 600 °C. The oxidation of the expansion agent and the densification of the composite take place between 300 and 800 °C.