Rapid thermal oxidation of porous silicon leads to desorbtion of hydrogen from the inner surface and formation of a thin oxide layer. Despite this dramatic change in the chemical composition oxidized microporous silicon (miPS) shows photoluminescence (PL) in the visible region. This is contradictory to the idea that the observed PL originates from chemical compounds like siloxene or polysilane, which would require a certain stoichiometry. If silicon microcrystallites are still present in the oxidized miPS, the observed luminescence can be explained in terms of a quantum confinement effect. It is the purpose of this work to prove the existence of microcrystallites in oxidized miPS using electron microscopy and X-ray diffraction.