The nanostructure and chemical distribution in semi-insulating polycrystalline oxygen-doped silicon (SIPOS) deposited on (001) Si and its isothermal transformation behavior at 900 °C were investigated by high resolution electron microscopy (HREM) and electron energy loss nanospectroscopy (EELS). The structure of the as-deposited film, which contained 15 at. % oxygen, was amorphous. No evidence for nanocrystalline second phases was found. It was similar in appearance to amorphous silicon. After annealing for 30 min at 900 °C in an inert environment (N 2 ), a dispersion of small nanocrystals, identified as silicon by imaging, diffraction and EELS, formed in the amorphous SIPOS matrix, with a thin precipitate free zone (PFZ) adjacent to the Si substrate. The SIPOS matrix oxygen concentration increased to 36 at. % and the matrix remained amorphous after annealing. No other phases were observed in annealed specimens. Changes in S i -L near edge fine structure and low loss peaks in EELS spectra from SIPOS with increasing oxygen concentration indicated that it is a solid solution supersaturated with silicon. Microstructures indicated that the Si nanocrystals formed during a homogeneous precipitation reaction.