We present an x-ray scattering study of the temperature-induced phase separation and Si nanocrystal formation in bulk amorphous SiOx with x≈1. X-ray Raman scattering at the Si LII,III-edge reveals a significant contribution of suboxides present in native amorphous SiO. The suboxide contribution decreases with increasing annealing temperature between 800–1200 °C pointing toward a phase separation of SiO into Si and SiO2 domains. In combination with x-ray diffraction and small angle x-ray scattering the SiO microstructure is found to be dominated by internal suboxide interfaces in the native state. For higher annealing temperatures above 900 °C growth of Si nanocrystals with rough surfaces embedded in a silicon oxide matrix can be observed.