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The SrFeO3/SiO2/Si thin film system has been studied using transmission electron microscopy (TEM). The thin films of SrFeO3 were grown by pulsed laser deposition onto silicon substrates with a SiO2 buffer layer at room temperature (RT) and 700 °C and subjected to annealing for various periods of time at temperature T = 700 °C. Transmission electron microscopy characterization showed that the microstructure of the film deposited at room temperature contained crystalline and amorphous layers. Silicon diffusion into SrFeO3 films occurred at the SiO2 interface for the samples deposited at 700 °C and for those films annealed at 700 °C. The silicon diffusion-induced interfacial reactions resulted in the phase transformations and the growth of complex crystalline and amorphous phases. The principal compositions of these phases were Sr(Fe,Si)12O19, SrOx and amorphous [Sr-Fe-O-Si].