Sponge-like Si nanostructures embedded in SiO₂ were fabricated by spinodal decomposition of sputter-deposited silicon-rich oxide with a stoichiometry close to that of silicon monoxide. After thermal treatment a mean feature size of about 3 nm was found in the phase-separated structure. The structure of the Si-SiO₂ nanocomposite was investigated by energy-filtered transmission electron microscopy (EFTEM), EFTEM tomography, and atom probe tomography, which revealed a percolated Si morphology. It was shown that the percolation of the Si network in 3D can also be proven on the basis of 2D EFTEM images by comparison with 3D kinetic Monte Carlo simulations.