High-temperature post-oxidation annealing of poly-Si/SiO2/Si structures such as metal-oxidesemiconductor capacitors and metal-oxide-semiconductor field effect transistors is known to result in enhanced radiation sensitivity, increased 1/f noise, and low field breakdown. We have studied the origins of these effects from a spectroscopic standpoint using electron paramagnetic resonance (EPR) and atomic force microscopy. One result of high temperature annealing is the generation of three types of paramagnetic defect centers, two of which are associated with the oxide close to the Si/SiO2 interface (oxygen-vacancy centers) and the third with the bulk Si substrate (oxygen-related donors). In all three cases the origin of the defects may be attributed to out-diffusion of O from the SiO2 network into the Si substrate with associated reduction of the oxide. We present a straightforward model for the interfacial region which assumes the driving force for O out-diffusion is the chemical potential difference of the O in the two phases (SiO2 and the Si substrate). Experimental evidence is provided to show that enhanced hole trapping and interface-trap and border-trap generation in irradiated high-temperature annealed Si/SiO2/Si systems are all related either directly, or indirectly, to the presence of oxygen vacancies.