The thermal stability of epitaxial silicon‐carbon alloys grown by molecular beam epitaxy on (001) silicon was investigated using high resolution x‐ray diffraction, transmission electron microscopy, and secondary ion mass spectroscopy measurements. Different superlattices, with alloy compositions of Si0.997C0.003, Si0.992C0.008, and Si0.985C0.015, all nominally 6 nm thick, with 24 nm Si spacer layers were employed. Annealing studies determined that there are different pathways to strain relaxation in this material system. At annealing temperatures of 900 °C and below, the structures relax only by interdiffusion, indicating that these layers are stable during typical device processing steps. At temperatures of 1000 °C and above, SiC precipitation dominates with enhanced precipitation in the Si1−xCx layers with the highest initial carbon content.